CN116234891A

CN116234891A - Aryloxyalkylamines as fuel additives for reducing injector fouling in direct injection spark ignition gasoline engines

Info

Publication number: CN116234891A
Application number: CN202180066654.2A
Authority: CN
Inventors: M·K·恩格; R·E·切派克; C·Y·陈; K·门登霍尔; A·M·埃斯科斯; P·A·富恩特斯-阿弗莱克; J·王
Original assignee: Chevron USA Inc; Chevron Oronite Co LLC
Current assignee: Chevron USA Inc; Chevron Oronite Co LLC
Priority date: 2020-09-17
Filing date: 2021-09-15
Publication date: 2023-06-06
Also published as: EP4214297A1; AU2021342779A1; KR20230068407A; WO2022058894A1; US20240026239A1; MX2023003074A; JP2023541471A; CA3195345A1; CO2023004450A2

Abstract

A fuel composition is described. The composition contains gasoline and an aryloxyalkylamine additive. The structure of the aryloxyalkylamine additive is given by formula (I)

Wherein the aryloxyalkylamine additive is present in about 10 to about 750ppm by weight based on the total weight of the fuel composition. X is a hydrocarbon group having 1 or 2 carbon atoms. R is R ¹ And R is ² Independently hydrogen or a substituted hydrocarbyl group having up to 36 carbon atoms.

Description

Aryloxyalkylamines as fuel additives for reducing injector fouling in direct injection spark ignition gasoline engines

Technical Field

The present disclosure relates to fuel additives and dye compositions containing the dye additives. More specifically, the present disclosure describes compositions and methods for controlling deposit formation in direct injection spark ignition gasoline engines.

Background

Conventional fuel additives developed for Port Fuel Injection (PFI) gasoline engines are generally not optimized for controlling deposit formation in injectors of direct injection spark ignition (dis) engines, sometimes referred to as Direct Injection Gasoline (DIG) or Gasoline Direct Injection (GDI) engines. This is mainly because unlike PFI engines, dis engines deliver fuel directly into the combustion chamber. When the fuel is directly injected, it is immediately exposed to high temperatures and pressures. In such an environment, combustion products may accumulate on the outer and/or inner surfaces of the injector and nozzle (referred to as injector fouling).

The formation of deposits around the injector nozzles and inside the combustion chamber may have a significant negative impact on one or more of fuel flow rate, injection duration, and/or injection pattern. This, in turn, may result in increased emissions, increased Particulate Matter (PM) formation, reduced fuel economy, power/performance losses, increased wear, and/or reduced equipment life.

Disclosure of Invention

In one aspect, a fuel composition is provided, the fuel composition comprising gasoline; and an aryloxyalkylamine additive having the structure:

wherein the aryloxyalkylamine additive is present in about 10 to about 750ppm by weight based on the total weight of the fuel composition; wherein X is a hydrocarbon group having 1 or 2 carbon atoms; and wherein R is ¹ And R is ² Independently hydrogen or a hydrocarbon group having up to 36 carbon atoms.

In another aspect, there is provided a concentrate composition comprising about 0 to 90wt% of an organic solvent boiling in the range of 65 to 205 ℃ and about 10 to 100wt% of a fuel additive comprising: aryloxyalkylamines of the formula

Wherein X is a hydrocarbon group having 1 or 2 carbon atoms; and wherein R is ¹ And R is ² Independently hydrogen or a substituted hydrocarbyl group having up to 36 carbon atoms.

In another aspect, a method of reducing injector fouling in a direct injection spark ignition gasoline engine is provided, the method comprising providing a gasoline composition comprising: aryloxyalkylamine additives having the following structure

Wherein the aryloxyalkylamine additive is about 10 to about 10 by weight based on the total weight of the fuel compositionAbout 750ppm present; wherein X is a hydrocarbon group having 1 or 2 carbon atoms; and wherein R is ¹ And R is ² Independently hydrogen, substituted alkyl or alkenyl having up to 36 carbon atoms.

Drawings

Fig. 1 shows a diagram described in the embodiment.

Figures 2A-2C show photographs described in the examples.

Detailed Description

Compositions and methods for deposit control in direct injection engines are described. More particularly, the present invention provides detergent additive compositions useful as components of fuel compositions and methods of using the same.

The fuel composition of the present invention comprises (i) a hydrocarbon-based fuel; and (ii) an aryloxyalkylamine fuel additive. In some embodiments, the fuel composition may comprise an auxiliary fuel additive.

Hydrocarbon-based fuels

Hydrocarbon-based fuels include gasoline and diesel.

The gasoline fuel is at least mainly C ₄ -C ₁₂ A composition of hydrocarbons. In one embodiment, gasoline or gasoline boiling range components are further defined as meaning containing at least predominantly C ₄ -C ₁₂ Hydrocarbons and further have a boiling range of from about 37.8 ℃ (100°f) to about 204 ℃ (400°f). In an alternative embodiment, gasoline is defined to mean a gasoline containing at least predominantly C ₄ -C ₁₂ Hydrocarbons, having a boiling range from about 37.8 ℃ (100°f) to about 204 ℃ (400°f) and are further defined as compositions conforming to ASTM D4814.

Diesel fuel means that it contains at least mainly C ₁₀ -C ₂₅ Hydrocarbon middle distillate fuels. In one embodiment, diesel is further defined as meaning at least predominantly comprising C ₁₀ -C ₂₅ Hydrocarbons and further have a boiling range from about 165.6 ℃ (330°f) to about 371.1 ℃ (700°f). In an alternative embodiment, diesel is defined as above to mean that it contains at least predominantly C ₁₀ -C ₂₅ Hydrocarbon and toolHas a boiling range of from about 165.6 ℃ (330°f) to about 371.1 ℃ (700°f) and is further defined as a composition conforming to ASTM D975.

The hydrocarbon-based fuel is present in a major amount, based on the weight percent of the total fuel composition. In some embodiments, the hydrocarbon-based fuel is present in any range between about 50wt% or greater, 55wt% or greater, 60wt% or greater, 65wt% or greater, 70wt% or greater, 75wt% or greater, 80wt% or greater, 85wt% or greater, 90wt% or greater, 95wt% or greater, or about 50wt% to no more than 100 wt%.

According to some embodiments, the gasoline employed in the present invention may be Clean Burning Gasoline (CBG). CBG refers to gasoline formulations containing reduced levels of sulfur, aromatics and olefins. The exact formulation may vary depending on the local regulatory definition.

Fuel-soluble non-volatile carrier fluids (carrier fluids) or oils may also be used with the compounds of the present disclosure. The carrier fluid is a chemically inert hydrocarbon-soluble liquid carrier that significantly increases the non-volatile residue (NVR) or solvent-free liquid fraction of the fuel additive composition while not greatly promoting an increase in octane requirement. The carrier fluid may be a natural or synthetic oil such as mineral oil, refined petroleum, synthetic polyalkanes and olefins, including hydrogenated and unhydrogenated polyalphaolefins, synthetic polyoxyalkylene derived oils such as U.S. patent nos. 3,756,793, 4,191,537 and 5,004,478; and those described in european patent application publications 356,726 and 382,159.

The carrier fluid may be used in an amount ranging from 35 to 5000ppm by weight of the hydrocarbon fuel (e.g., 50 to 3000ppm of the fuel). When used in a fuel concentrate, the carrier fluid can be present in an amount ranging from 20 wt% to 60wt% (e.g., 30 wt% to 50 wt%).

Aryloxyalkylamine fuel additives

The aryloxyalkylamine fuel additive of the invention reduces injector fouling in direct injection spark ignition gasoline engines. The additive is a nitrogen-containing detergent having the formula:

wherein R is ¹ And R is ² Independently hydrogen or a hydrocarbon group having up to 36 carbon atoms. R is R ² May be ortho or meta with respect to the oxygen atom. X is a hydrocarbon group having 1 or 2 carbon atoms. X may be saturated or unsaturated. In some embodiments, R ¹ Or R is ² One of which may preferably be a hydrocarbon group and the other may be hydrogen.

In some embodiments, the hydrocarbyl group is an alkyl or alkenyl group. Alkyl refers to a saturated hydrocarbon group which may be straight chain, branched, cyclic or a combination of cyclic, straight chain and/or branched. Alkenyl refers to an unsaturated hydrocarbon group that may be straight chain, branched, cyclic or a combination of cyclic, straight chain and/or branched.

Suitable examples of aryloxyalkylamines include, but are not limited to, 2- (phenoxy) ethyl-1-amine, 2- (4-butylphenoxy) ethyl-1-amine, 2- (4-octylphenoxy) ethyl-1-amine, 2- (4-nonylphenoxy) ethyl-1-amine, 2- (4-dodecylphenoxy) ethyl-1-amine, 2- (4-octadecylphenoxy) ethyl-1-amine, 2- (4-eicosylphenoxy) ethyl-1-amine, 2- (4-docosylphenoxy) ethyl-1-amine, 2- (4-tetracosylphenoxy) ethyl-1-amine.

Aryloxyalkylamines are commercially available or obtained by any known synthetic method compatible therewith. For example, aryloxyalkylamines may be obtained by reacting a salt of an alkylphenol with chloroacetaldehyde. The resulting product is then reacted with an amino alcohol and then hydrogenated in the presence of a nickel catalyst to produce an aryloxyalkylamine. A more detailed description of aryloxyalkylamine synthesis can be found in U.S. patent No. 3,954,872, which is hereby incorporated by reference.

Synthesis

In general, the fuel additives of the present invention may be synthesized by any known compatible method. A description of two known synthetic methods is described herein.

In the first process (process a), an alkylphenol is first reacted with a base (e.g., potassium hydroxide) to form an alkylphenol salt, which will further react with 2-oxazolidinone in an aromatic solvent under reflux conditions to provide the corresponding aminoethylated product.

Method A

In the second process (process B), the alkylphenol is also first reacted with a base (e.g., potassium hydroxide) to form an alkylphenol salt, which will further react with the 2-oxazolidinone formed in situ from the reaction between ethanolamine and diethyl carbonate in an aromatic solvent under reflux conditions to provide the corresponding aminoethylated product.

Method B

The following examples of method B are provided for illustrative purposes.

A1000 mL two-necked round bottom flask equipped with a mechanical stirrer, dean-Stark trap and reflux condenser was charged with 4-eicosylphenol, 4-docosylphenol, 4-tetracosylphenol, 2-eicosylphenol, a mixture of 2-docosylphenol and 2-tetracosylphenol (120 g,0.298mol,1.00 eq), KOH (2.96 g,0.0447mol,0.150 eq, 85% active), 150mL of an aromatic 100 solvent, and the reaction was refluxed under vigorous stirring and a nitrogen purge for 1 hour to remove water. The reaction mixture was cooled to about 120℃and ethanolamine (21.87 g,0.358mol,1.20 eq.) and diethyl carbonate (42.3 g,0.358mol,1.20 eq.) were added sequentially. The reaction mixture was then quenched at gentle N ₂ Flow down to 120 ℃ until the theoretical amount of ethanol is discharged from the reaction, thenIt was warmed to 175 ℃ under vigorous stirring under a gentle stream of nitrogen for 19 hours. The crude reaction mixture was diluted with 250mL ethyl acetate and washed with 3x200mL water and 200mL brine. The organic layer was dried over MgSO ₄ Drying, filtration and concentration gave the crude product as an amber oil (128.0 g). It was analyzed by NMR spectroscopy and HPLC.

Auxiliary fuel additive

The fuel composition of the present invention comprises one or more auxiliary fuel additives. The secondary fuel additive is a nitrogen-containing detergent that provides enhanced cleanliness when paired with the primary fuel additive of the present invention.

Suitable co-fuel additives can be divided into aliphatic hydrocarbyl-substituted amines, hydrocarbyl-substituted poly (alkylene oxide) amines, hydrocarbyl-substituted succinimides, mannich reaction products, polyalkylphenoxy amino alkanes, nitro and amino aromatic esters of polyalkylphenoxy alkanols, and nitrogen-containing vaporizer/injector cleaners. Each type of auxiliary fuel additive will be described in more detail herein.

In particular, the aliphatic hydrocarbyl-substituted amines useful in the invention can be straight or branched chain hydrocarbyl-substituted amines having at least one basic nitrogen, and wherein the hydrocarbyl group has a number average molecular weight of about 700 to 3,000. Specific examples of aliphatic hydrocarbyl-substituted amines include polyisobutenyl amines and polyisobutyl amines. These amines may be derived as mono-or polyamines. The preparation of aliphatic amines is generally known and described in detail in U.S. patent No. 3,438,757; 3,565,804; 3,574,576; 3,848,056; 3,960,515; no. 4,832,702; and 6,203,584, which are incorporated by reference in their entirety.

In particular, the hydrocarbyl-substituted poly (oxyalkylene) amines (also referred to as "polyetheramines") useful in the present invention can include hydrocarbyl poly (oxyalkylene) amines (monoamines or polyamines) wherein the hydrocarbyl group contains from about 1 to about 30 carbon atoms. The number of alkylene oxide units may range from about 5 to about 100. The amine moiety is derived from ammonia, a primary alkyl or secondary dialkyl monoamine, or a polyamine having a terminal amino nitrogen atom. The alkylene oxide moiety may be propylene oxide or butylene oxide or mixtures thereof. Hydrocarbyl-substituted poly (oxyalkylene) amines are described in U.S. patent No. 6,217,624 and U.S. patent No. 5,112,364, which are hereby incorporated by reference. Specific examples of hydrocarbyl-substituted poly (oxyalkylene) monoamines include alkylphenyl poly (oxyalkylene) monoamines wherein the poly (oxyalkylene) moiety contains oxypropylene units or oxybutylene units or mixtures of oxypropylene and oxybutylene units. The alkyl group on the alkylphenyl moiety is a straight or branched chain alkyl group having from about 1 to about 24 carbon atoms. The preferred alkylphenyl moiety is tetrapropylphenyl, wherein the alkyl group is a branched chain alkyl group having 12 carbon atoms derived from a propylene tetramer.

More specifically, additional hydrocarbyl-substituted poly (oxyalkylene) amines are included in U.S. patent No. 4,288,612; 4,236,020; 4,160,648; 4,191,537; 4,270,930; 4,233,168; 4,197,409; the hydrocarbyl-substituted poly (oxyalkylene) urethanes disclosed in 4,243,798 and 4,881,945, which are hereby incorporated by reference. These hydrocarbyl poly (oxyalkylene) urethanes contain at least one basic nitrogen atom and have an average molecular weight of from about 500 to 10,000, preferably from about 500 to 5,000 and more preferably from about 1,000 to 3,000. The preferred carbamates are alkylphenyl poly (butylene oxide) carbamates in which the amine moiety is derived from ethylenediamine or diethylenetriamine.

In particular, hydrocarbyl-substituted succinimides useful in the present invention include polyalkyl and polyalkenyl succinimides, where the polyalkyl or polyalkenyl group has an average molecular weight of about 500 to 5,000, preferably about 700 to 3,000. Hydrocarbyl-substituted succinimides are typically prepared by reacting a hydrocarbyl-substituted succinic anhydride with an amine or polyamine having at least one reactive hydrogen bonded to an amine nitrogen atom. Preferred hydrocarbyl-substituted succinimides include polyisobutenyl and polyisobutenyl succinimides and derivatives thereof. Hydrocarbyl-substituted succinimides are described in U.S. patent No. 5,393,309; 5,588,973; 5,620,486; 5,916,825; 5,954,843; 5,993,497; and 6,114,542 and uk patent 1,486,144, which are all hereby incorporated by reference.

In particular, the Mannich reaction products used in the present invention include products typically obtained from Mannich condensation of high molecular weight alkyl-substituted hydroxyaromatic compounds, amines containing at least one reactive hydrogen, and aldehydes. The high molecular weight alkyl-substituted hydroxyaromatic compounds are preferably polyalkylphenols such as polypropylphenol and polybutylphenol, especially polyisobutylphenol, wherein the polyalkyl groups have an average molecular weight of about 600 to 3,000. The amine reactant is typically a polyamine, such as an alkylene polyamine, especially an ethylene or polyethylene polyamine, e.g., ethylenediamine, diethylenetriamine, triethylenetetramine, and the like. The aldehyde reactant is typically a fatty aldehyde such as formaldehyde, including paraformaldehyde and formalin, and acetaldehyde. Preferred Mannich reaction products are obtained by condensing a polyisobutylphenol with formaldehyde and diethylenetriamine, wherein the polyisobutyl group has an average molecular weight of about 1,000. Mannich reaction products suitable for use in the present invention are described, for example, in U.S. Pat. Nos. 4,231,759 and 5,697,988, the disclosures of each of which are incorporated herein by reference.

Yet another class of detergent additives suitable for use in the present invention are polyalkylphenoxyamino alkanes. Preferred polyalkylphenoxyamino alkanes include those having the formula:

wherein R is ₅ Is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; r is R ₆ And R is ₇ Independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and a is an amino group, an N-alkylamino group having from about 1 to about 20 carbon atoms in the alkyl group, an N, N-dialkylamino group having from about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms. The polyalkylphenoxyaminoalkanes of formula II above and their preparation are described in detail in U.S. patent No. 5,669,939, which is hereby incorporated by reference.

Certain detergent mixtures are particularly useful as co-additives according to the present invention.

In some embodiments, a mixture of polyalkylphenoxyamino alkanes and poly (oxyalkylene) amines may be used. These mixtures are described in detail in U.S. patent No. 5,851,242, which is hereby incorporated by reference.

In some embodiments, mixtures of nitro and amino aromatic esters of polyalkyl phenoxy alkanols may be used. Preferred nitro and amino aromatic esters of polyalkyl phenoxy alkanols include those having the formula:

wherein: r is R ₈ Is nitro or- (CH) ₂ )-NR ₁₃ R ₁₄ Wherein R is ₁₃ And R is ₁₄ Independently hydrogen or lower alkyl having 1 to 6 carbon atoms; r is R ₉ Is hydrogen, hydroxy, nitro or-NR ₁₅ R ₁₆ Wherein R is ₁₅ And R is ₁₆ Independently hydrogen or lower alkyl having 1 to 6 carbon atoms; r is R ₁₀ And R is ₁₁ Independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and R is ₁₂ Is a polyalkyl group having an average molecular weight in the range of about 450 to 5,000. Aromatic esters of polyalkyl phenoxyalkanols shown in formula III above and their preparation are described in detail in U.S. patent No. 5,618,320, which is hereby incorporated by reference.

Mixtures of nitro and amino aromatic esters of polyalkyl phenoxy alkanols and hydrocarbyl-substituted poly (oxyalkylene) amines are also useful in the present invention. These mixtures are described in detail in U.S. patent No. 5,749,929, which is hereby incorporated by reference. Preferred hydrocarbyl-substituted poly (oxyalkylene) amines useful as detergent additives in the present invention include those having the formula:

wherein: r is R ₁₇ Is a hydrocarbyl group having from about 1 to about 30 carbon atoms; r is R ₁₈ And R is ₁₉ Each independently is hydrogen or lower alkyl having from about 1 to about 6 carbon atoms, and each R ₁₈ And R is ₁₉ At each of the-O-CHR ₁₈ -CHR ₁₉ -independently selected ones of the cells; m is from about 5 to about 100; b is an amino group, an N-alkylamino group having from about 1 to about 20 carbon atoms in the alkyl group, an N, N-dialkylamino group having from about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms; and m is an integer from about 5 to about 100. The above hydrocarbyl-substituted poly (oxyalkylene) amines of formula IV and their preparation are described in detail in U.S. patent No. 6,217,624, which is hereby incorporated by reference. The hydrocarbyl-substituted poly (oxyalkylene) amines of formula IV are preferably used alone or in combination with other detergent additives, particularly in combination with polyalkylphenoxyaminoalkanes or nitro and aminoaromatic esters of polyalkylphenoxyalkanols. More preferably, the detergent additive used in the present invention will be a combination of a hydrocarbyl-substituted poly (oxyalkylene) amine with a nitro and amino aromatic ester of a polyalkyl phenoxy alkanol. A particularly preferred hydrocarbyl-substituted poly (oxyalkylene) amine detergent additive is dodecylphenoxypoly (oxybutylene) amine, and a particularly preferred detergent additive combination is a combination of dodecylphenoxypoly (oxybutylene) amine and 4-polyisobutylphenoxyethyl para-aminobenzoate.

Another class of detergent additives suitable for use in the present invention includes nitrogen-containing vaporizer/injector detergents. The vaporizer/injector cleaner additive is typically a low molecular weight compound having a number average molecular weight of from about 100 to about 600 and having at least one polar moiety and at least one non-polar moiety. The non-polar moiety is typically a linear or branched alkyl or alkenyl group having from about 6 to about 40 carbon atoms. The polar moiety is typically nitrogen-containing. Typical nitrogen-containing polar moieties include amines (e.g., as described in U.S. patent No. 5,139,534 and PCT international publication No. WO 90/10051), etheramines (e.g., as described in U.S. patent No. 3,849,083 and PCT international publication No. WO 90/10051), amides, polyamides, and amide esters (e.g., as described in U.S. patent No. 2,622,018; 4,729,769; and 5,139,534; and european patent publication No. 149,486), imidazolines (e.g., as described in U.S. patent No. 4,518,782), amine oxides (e.g., as described in U.S. patent No. 4,810,263 and 4,836,829), hydroxylamines (e.g., as described in U.S. patent No. 4,409,000), and succinimides (e.g., as described in U.S. patent No. 4,292,046). Each of these references is hereby incorporated by reference.

Each auxiliary fuel additive may be present at about 50ppm to about 2500ppm (e.g., 100 to 2000, 200 to 1500, 300 to 1000, etc.) by weight of the fuel composition. More preferably, the auxiliary fuel additive is present at about 50ppm to about 1000ppm by weight of the fuel composition.

Other additives

The fuel composition may contain other known fuel additives. Suitable examples include, but are not limited to, antioxidants, metal deactivators, demulsifiers, oxygenates, antiknock agents, dispersants, and other detergents. In diesel fuel, other well known additives may be used, such as pour point depressants (pour point depressant), flow improvers, and the like.

Each of the foregoing additives, when used, is used in a functionally effective amount to impart the desired properties to the fuel composition. Typically, the concentration of each of these additives, when used, may range from about 0.001 wt% to about 20 wt%, such as from about 0.01 wt% to about 10 wt%, unless otherwise indicated.

Concentrate

The compounds of the present disclosure may be formulated as concentrates using inert stable lipophilic (i.e., soluble in hydrocarbon fuels) organic solvents that boil in the range of 65 ℃ to 205 ℃. Aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene, or high boiling aromatic hydrocarbons or aromatic diluents may be used. Aliphatic alcohols containing 2 to 8 carbon atoms such as ethanol, isopropanol, methyl isobutyl methanol, n-butanol, and the like in combination with hydrocarbon solvents are also suitable for use with the additives of the present invention. The amount of additive in the concentrate may be in the range of 10 wt.% to 70 wt.% (e.g., 20 wt.% to 40 wt.%).

The following illustrative examples are intended to be non-limiting.

Examples

Inventive example 1

Inventive example 1 is 2- (4-dodecylphenoxy) ethyl-1-amine (formula V) shown below.

In a 2L three-necked round bottom flask, 4-dodecylphenol (200.0 g,0.76 mol) was dissolved in 1000mL of naphtha (aromatic 100) solvent. To this mixture was added potassium hydroxide (4.3 g), then hexanol (78 g,0.76 mol) and the resulting mixture was stirred at room temperature under nitrogen for 30 minutes using a mechanical stirrer. The mixture was then heated to reflux (about 165 ℃ C. -170 ℃ C.) and stirred under nitrogen for an additional 2 hours. During this period, the distillate (e.g., water/hexanol and aromatic solvent) was collected in a dean-stark trap apparatus. After stirring for 2 hours, the mixture was cooled to 120 ℃ and 2-oxazolidinone (66.0 g,0.76 mol) was added. The mixture was heated under reflux and stirred under nitrogen for 18 hours (overnight). The mixture was cooled to room temperature, diluted with hexane (100 mL), and the organic phase was washed with water (200 mL), brine (4 x100 mL), over anhydrous MgSO ₄ Dried and filtered through a pad of celite filter aid. The filtrate was concentrated under reduced pressure, then under high vacuum to give an amber oil (240 g) as crude product.

Inventive example 2

Inventive example 2 is a mixture of 2- (4-eicosylphenoxy) ethyl-1-amine, 2- (4-docosylphenoxy) ethyl-1-amine and 2- (4-tetracosylphenoxy) ethyl-1-amine shown below (formula VI). It is obtained by the method a described below.

Average molecules in a 2L 3-neck round bottom flaskA mixture of 4-eicosylphenol, 4-docosylphenol, 4-tetracosylphenol, 2-eicosylphenol, 2-docosylphenol and 2-tetracosylphenol (151.71 g,0.377 mol) in an amount of 402.71g/mol was dissolved in an aromatic 100 solvent (700 mL). To this mixture was added potassium hydroxide (2.1 g), then hexanol (38.5 g,0.377 mol) and the resulting mixture was stirred at room temperature under nitrogen atmosphere using a mechanical stirrer for 30 minutes. The mixture was then heated to reflux (about 165 ℃ C. -170 ℃ C.) and stirred under nitrogen for an additional 2 hours. During this period, the distillate (e.g., water/hexanol and aromatic solvent) was collected in a dean-stark trap apparatus. After stirring for 2 hours, the mixture was cooled to 120 ℃ and 2-oxazolidinone (32.77 g,0.377 mol) was added. The mixture was heated under reflux and stirred under nitrogen for 18 hours (overnight). The mixture was cooled to room temperature, diluted with hexane (200 mL), and the organic phase was washed with water (200 mL), brine (4 x100 mL), over anhydrous MgSO ₄ Dried and filtered through a pad of celite filter aid. The filtrate was concentrated under reduced pressure, then under high vacuum to give a dark oil (150.2 g) as crude product. The crude product was purified by column chromatography using a gradient of ethyl acetate/methanol mixture to give a pale yellow oil (105.8 g).

Inventive example 3

Inventive example 3 is commercially available 2= (phenoxy) ethyl-1-amine (formula VII) shown below.

Inventive example 4

4-nonylphenol (200.0 g, 0.258 mol) was dissolved in an aromatic 100 solvent (500 mL) in a 2L 3-neck round bottom flask. To this mixture was added potassium hydroxide (2.1 g) followed by hexanol (92.74 g, 0.90)8 mol) and the resulting mixture was stirred at room temperature under nitrogen for 30 minutes using a mechanical stirrer. The mixture was then heated to reflux (about 165 ℃ C. -170 ℃ C.) and stirred under nitrogen for an additional 2 hours. During this period, the distillate (e.g., water/hexanol and aromatic solvent) was collected in a dean-stark trap apparatus. After stirring for 2 hours, the mixture was cooled to 120 ℃ and 2-oxazolidinone (102.75 g,1.180 mol) was added. The mixture was heated under reflux and stirred under nitrogen for 18 hours (overnight). The mixture was cooled to 70 ℃ and ethylenediamine (10.91 g,0.182 mol) was added and the mixture was heated at reflux for 4 hours. The mixture was cooled to room temperature and added

(100g) And stirred for 30 minutes. The mixture was filtered and concentrated under high vacuum to give the crude product as a pale yellow oil (243.67 g). The crude product was further washed with water (3×500 mL), brine (500 mL), over anhydrous MgSO ₄ Dried and filtered through a pad of celite filter aid. The filtrate was concentrated under reduced pressure, then concentrated under vacuum. The crude product was purified by column chromatography using a gradient of ethyl acetate/methanol mixture to give a pale yellow oil.

Embodiments of the present invention were blended in gasoline and tested for their ability to mitigate DISI direct injector fouling in test vehicles. A 2017 VW jettase vehicle equipped with a 1.4l 16 valve turbocharged dis engine was used as the test vehicle.

Fig. 1 shows a vehicle speed condition observed during a specified vehicle travel cycle. The vehicle drive cycle is based on 10 ramps extracted from the transient phase of the Environmental Protection Agency (EPA) city dynamometer drive schedule (UDDS) with the addition of an additional idle period. The total drive cycle was 20 minutes duration and the total test duration was 2,000 miles.

Additive testing was performed in a "keep clean" configuration starting with a clean injector and combustion chamber. This test configuration evaluates the ability of a given deposit control additive to keep injectors and combustion chambers clean during the test duration.

Injector "keep clean" tests were performed on four fuel samples: (i) non-added base fuel, (ii) 200ppmw of inventive example 1 added to sample (i), (iii) 200ppmw of inventive example 2 added to sample (i), and (iv) 200ppmw of inventive example 3 added to sample (i).

A set of four cleaning injectors was used at the beginning of each vehicle test. At the end of the test, a photograph of the formed deposit of four ejectors was taken. Fig. 2 shows photographs of the injector before and after the engine test.

The flow restriction of the injector was also measured. Table 1 shows the average injector flow limit (%) measured at the end of the engine test as compared to the base fuel reference (i.e., no gasoline added).

As shown, inventive example 1 provided a much lower flow restriction (0.39% on average) when compared to the base fuel reference (2.81% on average). Inventive examples 2 and 3 also provided lower flow restrictions (average 1.47% and 2.15%, respectively)

Injector fuel limit measures the decrease in fuel flow from the injector, indicating the presence of deposits in the injector orifice. Injector limitations may force additional control adjustments to the engine controller to maintain proper engine fuel delivery, and the presence of deposits in the injector orifices may affect fuel mixing, resulting in reduced engine performance and increased particulate emissions.

TABLE 1

A second test was also performed using the engine on the dynamometer bench. A 2017Honda DISI1.5L 16 valve turbocharged engine is the test vehicle engine used. The duration of the engine run cycle is 720 seconds, the engine speed ranges from idle to 4000RPM, and the load varies up to 160Nm. The total test duration was 50 hours (test duration with 200ppmw of the baseline fuel of example 2 was 25 hours). FIG. 3 illustrates engine speed and load test conditions.

A set of four cleaning injectors was used at the beginning of each engine test. At the end of the test, a photograph of the formed deposit of four ejectors was taken (fig. 4).

PM measurements were made on an engine test stand using an AVL Micro Smoke Sensor (MSS). MSS provides continuous, fast response measurements of solid particulate matter and is highly relevant to the gravimetric method of traditional PM measurements.

In the PM emission trace shown in FIG. 5 (the larger 3600 second portion of the 50 hour test), how fast PM emissions rise and fall with changing engine conditions can be observed. To provide useful metrics for such data, reference may be made to official measurement methods (e.g., federal test procedure or FTP in the united states) for use in regulatory vehicle emissions certification. In these cases, the regulatory body will simply report the aggregate total amount of emissions from the vehicle exhaust pipe throughout the drive cycle. Applying a similar strategy to the PM dataset we integrate PM emissions during one test driving cycle. This integration is then repeated for each driving cycle and a PM emission trend line is generated throughout the test duration.

Fig. 6A-6C show PM emission traces from a baseline fuel (fig. 6A), a baseline fuel having 200ppmw of inventive example 1 (fig. 6B), and a baseline fuel having 200ppmw of inventive example 2 (fig. 6C). The addition of 200ppmw of inventive example 1 or inventive example 2 maintained PM emissions at the same level as the use of a clean injector at the beginning of the test throughout the duration of the test.

All documents described herein are incorporated by reference to the extent they do not conflict with the present disclosure, including any priority documents and/or test procedures. As is apparent from the foregoing general description and specific embodiments, while forms of the disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the present disclosure be limited thereby.

For brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to list a range not explicitly listed, and a range from any lower limit may be combined with any other lower limit to list a range not explicitly listed, and a range from any upper limit may be combined with any other upper limit in the same manner. Furthermore, each point or individual value between its endpoints is included within a range even though not explicitly recited. Thus, each point or individual value may serve as its own lower or upper limit to be combined with any other point or individual value or any other lower or upper limit to enumerate ranges not explicitly recited.

Also, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that we also contemplate the same composition or group of elements having the transitional phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "being of" prior to the recitation of the composition, element, or plurality of elements, and vice versa.

The terms "a" and "an" and "the" as used herein are to be understood as covering both the plural and the singular.

Various terms have been defined above. If a term used in a claim is not defined above, a person skilled in the relevant art should be given the broadest definition of the term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

The foregoing description of the present disclosure illustrates and describes the present disclosure. Furthermore, the present disclosure shows and describes only the preferred embodiments, but as noted above, it is to be understood that the present disclosure is capable of use in various other combinations, modifications, and environments and is capable of changes or modifications within the scope of the concept as expressed herein, commensurate with the above teachings and/or the skill or knowledge of the relevant art. While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

It is to be understood that when a combination, subset, group, etc. of elements is disclosed (e.g., a combination of components in a composition, or a combination of steps in a method), each is specifically contemplated and described herein, although specific reference to each of the various individual and collective combinations and permutations of these elements may not be explicitly disclosed.

The embodiments described hereinabove are further intended to explain best modes known of practicing the invention and to enable others skilled in the art to utilize the disclosure in such, or other, embodiments and with the various modifications required by the particular applications or uses. Accordingly, the description is not intended to limit the invention to the form disclosed herein. Furthermore, it is intended that the appended claims be construed to include alternative embodiments.

Claims

1. A fuel composition comprising:

gasoline; and

an aryloxyalkylamine additive having the structure:

wherein the aryloxyalkylamine additive is present in about 10 to about 750ppm by weight based on the total weight of the fuel composition;

wherein X is a hydrocarbon group having 1 or 2 carbon atoms; and is also provided with

Wherein R is ¹ And R is ² Independently hydrogen or a substituted hydrocarbyl group having up to 36 carbon atoms.

2. The fuel composition of claim 1 wherein X is ethylene.

3. The fuel composition of claim 1, further comprising:

a nitrogen-containing cleaning agent.

4. A fuel composition as claimed in claim 3 wherein the nitrogen-containing detergent is an aliphatic hydrocarbyl amine, a hydrocarbyl-substituted poly (alkylene oxide) amine, a hydrocarbyl-substituted succinimide, a mannich reaction product, a nitro-and amino-aromatic ester of a polyalkyl phenoxy alkanol, or a polyalkylphenoxy amino alkane.

5. The fuel composition of claim 1, further comprising an antioxidant, a metal deactivator, a demulsifier, an oxygenate, an antiknock agent, a dispersant, a pour point depressant, or a flow improver.

6. The fuel composition of claim 1 wherein the aryloxyalkylamine is 2- (4-dodecylphenoxy) ethyl-1-amine, 2- (phenoxy) ethyl-1-amine, 2- (4-butylphenoxy) ethyl-1-amine, 2- (4-octylphenoxy) ethyl-1-amine, 2- (4-nonylphenoxy) ethyl-1-amine, 2- (4-octadecylphenoxy) ethyl-1-amine, 2- (4-eicosylphenoxy) ethyl-1-amine, 2- (4-docosylphenoxy) ethyl-1-amine, or 2- (4-tetracosylphenoxy) ethyl-1-amine.

7. A concentrate composition comprising:

about 10 to 90wt% of an organic solvent boiling in the range of 65 to 205 ℃; and;

about 10 wt% to 100wt% of a fuel additive comprising:

aryloxyalkylamines of the formula

Wherein R is ¹ And R is ² Independently hydrogen or having at mostSubstituted hydrocarbyl of 36 carbon atoms.

8. The concentrate composition of claim 7 wherein X is ethylene.

9. The concentrate composition of claim 7, further comprising:

a nitrogen-containing cleaning agent.

10. The concentrate composition of claim 9, wherein the nitrogen-containing detergent is an aliphatic hydrocarbyl amine, a hydrocarbyl-substituted poly (alkylene oxide) amine, a hydrocarbyl-substituted succinimide, a mannich reaction product, a nitro and amino aromatic ester of a polyalkyl phenoxy alkanol, or a polyalkylphenoxy amino alkane.

11. The concentrate composition of claim 7 wherein R ¹ And R is ² At least one of which is hydrogen.

12. The concentrate composition of claim 7, wherein the aryloxyalkylamine is 2- (4-dodecylphenoxy) ethyl-1-amine, 2- (phenoxy) ethyl-1-amine, 2- (4-butylphenoxy) ethyl-1-amine, 2- (4-octylphenoxy) ethyl-1-amine, 2- (4-nonylphenoxy) ethyl-1-amine, 2- (4-octadecylphenoxy) ethyl-1-amine, 2- (4-eicosylphenoxy) ethyl-1-amine, 2- (4-docosylphenoxy) ethyl-1-amine, or 2- (4-tetracosylphenoxy) ethyl-1-amine.

13. A method of reducing injector fouling in a direct injection spark ignition gasoline engine, the method comprising:

providing a gasoline composition comprising:

aryloxyalkylamine additives having the following structure

Wherein R is ¹ And R is ² Independently hydrogen, substituted alkyl or alkenyl having up to 36 carbon atoms.

14. The method of claim 13, wherein X is ethylene.

15. The method of claim 13, further comprising:

a nitrogen-containing cleaning agent.

16. The method of claim 13, wherein the nitrogen-containing detergent is an aliphatic hydrocarbyl amine, a hydrocarbyl-substituted poly (alkylene oxide) amine, a hydrocarbyl-substituted succinimide, a mannich reaction product, a nitro and amino aromatic ester of a polyalkyl phenoxy alkanol, or a polyalkylphenoxy amino alkane.

17. The method of claim 16, further comprising an antioxidant, a metal deactivator, a demulsifier, an oxygenate, an antiknock agent, a dispersant, a pour point depressant, or a flow improver.

18. The method of claim 13, wherein the aryloxyalkylamine is 2- (4-dodecylphenoxy) ethyl-1-amine, 2- (phenoxy) ethyl-1-amine, 2- (4-butylphenoxy) ethyl-1-amine, 2- (4-octylphenoxy) ethyl-1-amine, 2- (4-nonylphenoxy) ethyl-1-amine, 2- (4-octadecylphenoxy) ethyl-1-amine, 2- (4-eicosylphenoxy) ethyl-1-amine, 2- (4-docosylphenoxy) ethyl-1-amine, or 2- (4-tetracosylphenoxy) ethyl-1-amine.