Aryloxyalkyl amines as fuel additives for reducing injector fouling in direct injection spark-ignition gasoline engines

Abstract

A fuel composition is described. The composition contains gasoline and an aryloxyalkyl amine additive. The structure of the aryloxyalkyl amine additive is given by formula (I) wherein the aryloxyalkyl amine additive is present at about 10 to about 750 ppm by weight based on the total weight of the fuel composition. X is a hydrocarbyl group having 1 or 2 carbon atoms. R 1 and R 2 are independently hydrogen or a substituted hydrocarbyl group having up to 36 carbon atoms.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to fuel additives and dye compositions containing the same. More specifically, the present disclosure describes compositions and methods for controlling deposit formation in direct injection spark-ignition gasoline engines. BACKGROUND

[0002] 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 (DISI) engines, sometimes referred to as direct injection gasoline (DIG) or gasoline direct injection (GDI) engines. This is primarily because, unlike PFI engines, DISI engines deliver fuel directly into the combustion chamber. When fuel is injected directly, it is immediately exposed to high temperatures and pressures. In this environment, combustion products can accumulate on the outer and / or inner surfaces of the injector and nozzle, referred to as injector fouling.

[0003] The formation of deposits around the injector nozzle and inside the combustion chamber can have a significant negative impact on one or more of fuel flow rate, injection duration, and / or injection form. This in turn can result in increased emissions, increased particulate matter (PM) formation, reduced fuel economy, power / performance loss, increased wear, and / or shortened equipment life. SUMMARY

[0004] In one aspect, a fuel composition is provided, the fuel composition comprising gasoline; and an aryloxyalkyl amine additive having the structure:

[0005]

[0006] wherein the aryloxyalkyl amine additive is present at about 10 to about 750 ppm by weight based on the total weight of the fuel composition; wherein X is a hydrocarbyl group having 1 or 2 carbon atoms; and wherein R 1 and R 2 are independently hydrogen or a hydrocarbyl group having up to 36 carbon atoms.

[0007] In another aspect, a concentrate composition is provided, the concentrate composition comprising about 0 wt% to 90 wt% of an organic solvent boiling in the range of 65 °C to 205 °C and about 10 wt% to 100 wt% of a fuel additive, the fuel additive comprising: an aryloxyalkyl amine given by the formula

[0008]

[0009] wherein X is a hydrocarbyl group having 1 or 2 carbon atoms; and wherein R 1 and R 2independently is hydrogen or substituted alkyl or alkenyl having up to 36 carbon atoms.

[0010] 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: an aryloxyalkyl amine additive having the structure

[0011]

[0012] wherein the aryloxyalkyl amine additive is present at about 10 to about 750 ppm by weight based on the total weight of the fuel composition; wherein X is a hydrocarbyl group having 1 or 2 carbon atoms; and wherein R 1 and R 2 independently is hydrogen, substituted alkyl or alkenyl having up to 36 carbon atoms. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 The figures illustrated in the examples are shown.

[0014] Figure 2 The photographs illustrated in the examples are shown. DETAILED DESCRIPTION

[0015] The present invention describes compositions and methods for deposit control in direct injection engines. More specifically, the present invention provides a detergent additive composition useful as a component of a fuel composition and methods of using the same.

[0016] The fuel composition of the present invention comprises (i) a hydrocarbon-based fuel; and (ii) an aryloxyalkyl amine fuel additive. In some embodiments, the fuel composition can comprise ancillary fuel additives.

[0017] Hydrocarbon-based fuel

[0018] Hydrocarbon-based fuels include gasoline and diesel.

[0019] Gasoline fuel refers to a composition that is at least predominantly C4-C 12 hydrocarbons. In one embodiment, gasoline or a gasoline boiling range component is further defined to refer to a composition that is at least predominantly C4-C 12 hydrocarbons and further has a boiling range from about 37.8°C (100°F) to about 204°C (400°F). In an alternative embodiment, gasoline is defined to refer to a composition that is at least predominantly C4-C 12 hydrocarbons, has a boiling range from about 37.8°C (100°F) to about 204°C (400°F) and is further defined to comply with ASTM D4814.

[0020] Diesel fuel refers to a composition that is at least predominantly comprised of C 10 -C 25 hydrocarbons. In one embodiment, diesel is further defined to refer to a composition that is at least predominantly comprised of C 10 -C 25 hydrocarbons and further has a boiling range from about 165.6°C (330°F) to about 371.1°C (700°F). In alternative embodiments, diesel is defined as above to refer to a composition that is at least predominantly comprised of C 10 -C 25 hydrocarbons, has a boiling range from about 165.6°C (330°F) to about 371.1°C (700°F), and is further defined to meet ASTM D975.

[0021] The hydrocarbon-based fuel is present in a major amount by weight % of the total fuel composition. In some embodiments, the hydrocarbon-based fuel is present in a range of about 50 wt% or greater, 55 wt% or greater, 60 wt% or greater, 65 wt% or greater, 70 wt% or greater, 75 wt% or greater, 80 wt% or greater, 85 wt% or greater, 90 wt% or greater, 95 wt% or greater, or any range between about 50 wt% to less than 100 wt%.

[0022] According to some embodiments, the gasoline employed in the present application can be clean burning gasoline (CBG). CBG refers to a gasoline formulation containing reduced levels of sulfur, aromatics, and olefins. The exact formulation can vary depending on local regulatory definitions.

[0023] Fuel-soluble, non-volatile carrier fluids or oils can also be used with the compounds of the present disclosure. Carrier fluids are chemically inert, hydrocarbon-soluble liquid carriers that significantly increase the non-volatile residue (NVR) or solventless liquid fraction of the fuel additive composition, while not greatly promoting an increase in octane demand. The carrier fluids can be natural or synthetic oils, such as mineral oil, refined petroleum oil, synthetic polyalkanes and olefins, including hydrogenated and unhydrogenated polyalphaolefins, synthetic polyoxyalkylene derived oils such as those described in U.S. Patent Nos. 3,756,793; 4,191,537; and 5,004,478; and European Patent Application Publication Nos. 356,726 and 382,159.

[0024] The carrier fluid can be used in an amount ranging from 35 to 5000 ppm by weight of the hydrocarbon fuel (e.g., 50 to 3000 ppm of the fuel). When used in a fuel concentrate, the carrier fluid can be present in an amount ranging from 20 wt% to 60 wt% (e.g., 30 wt% to 50 wt%).

[0025] Aryloxyalkyl amine fuel additive

[0026] The aroxyalkyl amine fuel additive of the present invention reduces injector fouling in direct injection spark-ignition gasoline engines. The additive is a nitrogen-containing detergent having the formula:

[0027]

[0028]

[0029] where R 1 and R 2 are independently hydrogen or a hydrocarbyl group having up to 36 carbon atoms. R 2 may be located ortho or meta with respect to the oxygen atom. X is a hydrocarbyl group having 1 or 2 carbon atoms. X can be saturated or unsaturated. In some embodiments, R 1 or R 2 may preferably be a hydrocarbyl group and the other can be hydrogen.

[0030] In some embodiments, the hydrocarbyl group is an alkyl group or an alkenyl group. Alkyl refers to a saturated hydrocarbyl group, which can be linear, branched, cyclic, or a combination of cyclic, linear, and / or branched. Alkenyl refers to an unsaturated hydrocarbyl group, which can be linear, branched, cyclic, or a combination of cyclic, linear, and / or branched.

[0031] Suitable examples of aroxyalkyl amines 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.

[0032] Aroxyalkyl amines are commercially available or can be obtained by any known compatible synthetic method. For example, aroxyalkyl amines can be obtained by reacting a salt of an alkyl phenol with chloroacetaldehyde. The resulting product is then reacted with an amino alcohol, which is then hydrogenated in the presence of a nickel catalyst to produce the aroxyalkyl amine. A more detailed description of aroxyalkyl amine synthesis can be found in U.S. Patent No. 3,954,872, which is hereby incorporated by reference.

[0033] Synthesis

[0034] Generally, the fuel additive of the present invention can be synthesized by any known compatible method. Descriptions of two known synthetic methods are described herein.

[0035] In the first method (Method A), the alkyl phenol is first reacted with a base (e.g., potassium hydroxide) to form an alkyl phenoxide salt, which will be further reacted with a 2-oxazolidinone in an aromatic solvent under reflux conditions to provide the corresponding aminomethylation product.

[0036] Method A

[0037]

[0038] In the second method (Method B), the alkyl phenol is also first reacted with a base (e.g., potassium hydroxide) to form an alkyl phenoxide salt, which will be further reacted with a 2-oxazolidinone generated in situ from the reaction between ethanolamine and diethyl carbonate in an aromatic solvent under reflux conditions to provide the corresponding aminomethylation product.

[0039] Method B

[0040]

[0041] For illustrative purposes, the following example of Method B is provided.

[0042] A 1000 mL two necked round bottom flask, equipped with a mechanical stirrer, Dean-Stark trap and reflux condenser, was charged with a mixture of 4-icosylphenol, 4- docosylphenol, 4-tetracosylphenol, 2-icosylphenol, 2-docosylphenol and 2- tetracosylphenol (120 g, 0.298 mol, 1.00 equiv), average molecular weight 402.71 g / mol, KOH (2.96 g, 0.0447 mol, 0.150 equiv, 85% active), 150 mL of aromatic 100 solvent and the reaction mixture was refluxed under vigorous stirring and nitrogen purging atmosphere for 1 hour to remove water. The reaction mixture was cooled to about 120 °C and ethanolamine (21.87 g, 0.358 mol, 1.20 equiv) and diethyl carbonate (42.3 g, 0.358 mol, 1.20 equiv) were added sequentially. The reaction mixture was then warmed to 120 °C under mild N2flow until the theoretical amount of ethanol was evolved from the reaction, which was then warmed to 175 °C under mild nitrogen flow with vigorous stirring for 19 hours. The crude reaction mixture was diluted with 250 mL of ethyl acetate and washed with 3 x 200 mL of water and 200 mL of brine. The organic layer was dried over MgS04, filtered and concentrated to give the crude product as an amber colored oil (128.0 g). It was analyzed by NMR spectroscopy and HPLC.

[0043] Co-fuel additive

[0044] The fuel composition of the present invention comprises one or more co-fuel additives. The co-fuel additives are nitrogen-containing detergents that provide enhanced detergency when paired with the primary fuel additive of the present invention.

[0045] Suitable co-fuel additives can be classified as aliphatic hydrocarbyl-substituted amines, hydrocarbyl-substituted poly(oxyalkylene) amines, hydrocarbyl-substituted succinimides, Mannich reaction products, polyalkylphenoxy aminoalkanes, nitro and amino aromatic esters of polyalkylphenoxyalkanols, and nitrogen-containing carburetor / injector detergents. Each class of co-fuel additives will be described in greater detail herein.

[0046] In particular, the aliphatic hydrocarbyl-substituted amines used in the present invention can be linear or branched 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 can be derived as monoamines or polyamines. The preparation of aliphatic amines is generally known and described in detail in U.S. Patent Nos. 3,438,757; 3,565,804; 3,574,576; 3,848,056; 3,960,515; 4,832,702; and 6,203,584, all of which are hereby incorporated by reference.

[0047] In particular, the hydrocarbyl-substituted poly(oxyalkylene) amines (also known as "polyether amines") used 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 oxyalkylene units can 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 terminal amino nitrogen atoms. The oxyalkylene moiety can be propylene oxide or butylene oxide or a mixture 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 propylene oxide units or butylene oxide units or a mixture of propylene oxide and butylene oxide units. The alkyl group on the alkylphenyl moiety is a linear or branched alkyl group having from about 1 to about 24 carbon atoms. The preferred alkylphenyl moiety is a tetrapropylene phenyl group wherein the alkyl group is a branched alkyl group having 12 carbon atoms derived from the tetramerization of propylene.

[0048] More specifically, the additional hydrocarbyl-substituted poly(oxyalkylene) amines include the hydrocarbyl-substituted poly(oxyalkylene) aminocarbamates disclosed in U.S. Patent Nos. 4,288,612; 4,236,020; 4,160,648; 4,191,537; 4,270,930; 4,233,168; 4,197,409; 4,243,798; and 4,881,945, which are hereby incorporated by reference. These hydrocarbyl poly(oxyalkylene) aminocarbamates contain at least one basic nitrogen atom and have an average molecular weight of about 500 to 10,000, preferably about 500 to 5,000, and more preferably about 1,000 to 3,000. The preferred aminocarbamate is an alkylphenyl poly(oxybutylene) aminocarbamate, wherein the amine moiety is derived from ethylenediamine or diethylenetriamine.

[0049] In particular, the hydrocarbyl-substituted succinimides used in the present application include polyalkyl and polyalkenyl succinimides, wherein the polyalkyl or polyalkenyl group has an average molecular weight of about 500 to 5,000, preferably about 700 to 3,000. The 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 polyisobutyl succinimides and derivatives thereof. Hydrocarbyl-substituted succinimides are described in U.S. Patent Nos. 5,393,309; 5,588,973; 5,620,486; 5,916,825; 5,954,843; 5,993,497; and 6,114,542; and British Patent No. 1,486,144, all of which are hereby incorporated by reference.

[0050] In particular, the Mannich reaction products used in the present application include products obtained by Mannich condensation of a generally high molecular weight alkyl-substituted hydroxy aromatic compound, an amine containing at least one reactive hydrogen, and an aldehyde. The high molecular weight alkyl-substituted hydroxy aromatic compound is preferably a polyalkyl phenol, such as polypropyl phenol and polybutyl phenol, especially polyisobutyl phenol, where the polyalkyl group has an average molecular weight of about 600 to 3,000. The amine reactant is generally a polyamine, such as an alkylene polyamine, especially an ethylene or polyethylene polyamine, for example, ethylene diamine, diethylene triamine, triethylene tetramine, and the like. The aldehyde reactant is generally an aliphatic aldehyde, such as formaldehyde, including polyformaldehyde and formalin, and acetaldehyde. A preferred Mannich reaction product is obtained by condensing polyisobutyl phenol, where the polyisobutyl group has an average molecular weight of about 1,000, with formaldehyde and diethylene triamine. Mannich reaction products suitable for use in the present application are described, for example, in U.S. Patent Nos. 4,231,759 and 5,697,988, the disclosures of each of which are incorporated herein by reference.

[0051] Yet another class of detergent additives suitable for use in the present application is polyalkyl phenoxyl amino alkane. Preferred polyalkyl phenoxyl amino alkane include those having the formula:

[0052]

[0053] where R5 is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; R6 and R7 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and A is an amino group, an N-alkyl amino group having about 1 to about 20 carbon atoms in the alkyl group, an N,N-dialkyl amino group having about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having about 2 to about 12 amine nitrogen atoms and about 2 to about 40 carbon atoms. The polyalkyl phenoxyl amino alkane of formula II above and its preparation are described in detail in U.S. Patent No. 5,669,939, which is hereby incorporated by reference.

[0054] According to the present application, certain detergent mixtures can be used particularly as co-additives.

[0055] In some embodiments, mixtures of polyalkyl phenoxyl amino alkane and poly(oxyalkylene) amines can be used. These mixtures are described in detail in U.S. Patent No. 5,851,242, which is hereby incorporated by reference.

[0056] In some embodiments, mixtures of polyalkyl phenoxyl alkanoic acid nitrilo and amino aromatic esters can be used. Preferred polyalkyl phenoxyl alkanoic acid nitrilo and amino aromatic esters include those having the formula:

[0057] In some embodiments, mixtures of polyalkyl phenoxyl alkanoic acid nitrilo and amino aromatic esters can be used. Preferred polyalkyl phenoxyl alkanoic acid nitrilo and amino aromatic esters include those having the formula:

[0058] wherein: R8is nitro or— (CH2)— NR 13 R 14 wherein R 13 and R 14 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R9is hydrogen, hydroxy, nitro or— NR 15 R 16 wherein R 15 and R 16 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R 10 and R 11 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and R 12 is a polyalkyl having an average molecular weight in the range of about 450 to 5,000. The aromatic esters of polyalkylphenoxyalkanols shown above in Formula III and their preparation are described in detail in U.S. Patent No. 5,618,320, which is hereby incorporated by reference.

[0059] Mixtures of nitro and amino aromatic esters of polyalkylphenoxyalkanols and hydrocarbyl-substituted poly(oxyalkylene) amines can also be used in the present application. 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 which can be used as detergent additives in the present application include those having the formula:

[0060]

[0061] wherein: R 17 is a hydrocarbyl group having from about 1 to about 30 carbon atoms; R 18 and R 19 are each independently hydrogen or lower alkyl having from about 1 to about 6 carbon atoms, and each R 18 and R 19 is— O— CHR 18 — CHR 19— the units are independently selected; m is about 5 to about 100; B is an amino group, an N-alkylamino group having about 1 to about 20 carbon atoms in the alkyl group, an N,N-dialkylamino group having about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having about 2 to about 12 amine nitrogen atoms and about 2 to about 40 carbon atoms; and m is an integer of about 5 to about 100. The hydrocarbyl-substituted poly(oxyalkylene) amines of the above 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 polyalkylphenoxy aminoalkanes or nitro and amino aromatic esters of polyalkylphenoxy alkanols. More preferably, the detergent additive used in the present application will be a combination of a hydrocarbyl-substituted poly(oxyalkylene) amine and a nitro and amino aromatic ester of a polyalkylphenoxy alkanol. A particularly preferred hydrocarbyl-substituted poly(oxyalkylene) amine detergent additive is dodecylphenoxy poly(oxybutylene) amine, and a particularly preferred detergent additive combination is a combination of dodecylphenoxy poly(oxybutylene) amine and 4-polyisobutylphenoxyethyl p-aminobenzoate.

[0062] Another class of detergent additives suitable for use in the present application includes nitrogen-containing carburetor / injector detergents. Carburetor / injector detergent additives are typically low molecular weight compounds having a number average molecular weight of about 100 to about 600 and having at least one polar moiety and at least one nonpolar moiety. The nonpolar moiety is typically a linear or branched alkyl or alkenyl group having 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), ether amines (e.g., as described in U.S. Patent No. 3,849,083 and PCT International Publication No. WO 90 / 10051), amides, polyamides, and amidoesters (e.g., as described in U.S. Patent Nos. 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 Nos. 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.

[0063] Each co-fuel additive can be present in the range of about 50 ppm to about 2500 ppm (e.g., 100 to 2000, 200 to 1500, 300 to 1000, etc.) by weight of the fuel composition. More preferably, the co-fuel additive is present in the range of about 50 ppm to about 1000 ppm by weight of the fuel composition.

[0064] Other additives

[0065] The fuel composition can include other well-known fuel additives. Suitable examples include, but are not limited to, antioxidants, metal deactivators, demulsifiers, oxygenates, anti-knock agents, dispersants, and other detergents. In diesel fuel, other well-known additives can be used, such as pour point depressants, flow improvers, and the like.

[0066] Each of the foregoing additives is used in a functionally effective amount when used to impart the desired properties to the fuel composition. Generally, unless otherwise indicated, each of these additives is used in a concentration, when used, in the range of about 0.001 wt.% to about 20 wt.%, such as about 0.01 wt.% to about 10 wt.%.

[0067] Concentrate

[0068] The compounds of the present disclosure can be formulated as a concentrate using an inert stable lipophilic (i.e., soluble in hydrocarbon fuels) organic solvent that boils in the range of 65 °C to 205 °C. Aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene, or high-boiling aromatic hydrocarbons or aromatic diluents can be used. Aliphatic alcohols containing 2 to 8 carbon atoms such as ethanol, isopropyl alcohol, methyl isobutyl carbinol, n-butyl alcohol, and the like in combination with a hydrocarbon solvent are also suitable for use with the additives of the present invention. In the concentrate, the amount of additive can range from 10 wt.% to 70 wt.% (e.g., 20 wt.% to 40 wt.%).

[0069] The following illustrative examples are intended to be non-limiting.

[0070] Example

[0071] Inventive Example 1

[0072] Inventive Example 1 is 2-(4-dodecylphenoxy)ethyl-1-amine (Formula V) shown below.

[0073] In a 2 L three necked round bottom flask, 4-dodecylphenol (200.0 g, 0.76 mol) was dissolved in 1000 mL of naphtha (aromatic 100) solvent. To this mixture was added potassium hydroxide (4.3 g), followed by hexanol (78 g, 0.76 mol), and the resulting mixture was stirred at room temperature under a nitrogen atmosphere using a mechanical stirrer for 30 minutes. The mixture was then heated to reflux (about 165-170 °C) and stirred under nitrogen for an additional 2 hours. During this time period, distillate (e.g., water / hexanol and aromatic solvent) was collected in a Dean-Stark trap apparatus. After 2 hours of stirring, the mixture was cooled to 120 °C and 2-oxazolidinone (66.0 g, 0.76 mol) was added. The mixture was heated at 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 x 100 mL), dried over anhydrous MgS04, and filtered through a pad of celite filter aid. The filtrate was concentrated under reduced pressure, then concentrated under high vacuum to give an amber colored oil as a crude product (240 g).

[0074]

[0075] Inventive Example 2

[0076] Inventive Example 2 is a mixture of 2-(4-icosylphenoxy)ethyl-l-amine, 2-(4- docosylphenoxy)ethyl-l-amine, and 2-(4-tetracosylphenoxy)ethyl-l-amine (Formula VI) shown below. It was obtained by Method A described below.

[0077] A mixture of 4-icosylphenol, 4-docosylphenol, 4-tetracosylphenol, 2-icosylphenol, 2-docosylphenol, and 2-tetracosylphenol (151.71 g, 0.377 mol) having an average molecular weight of 402.71 g / mol was dissolved in aromatic 100 solvent (700 mL) in a 2 L 3 -necked round bottom flask. To this mixture was added potassium hydroxide (2.1 g), followed by hexanol (38.5 g, 0.377 mol), and the resulting mixture was stirred at room temperature under a nitrogen atmosphere using a mechanical stirrer for 30 minutes. The mixture was then heated to reflux (about 165-170 °C) and stirred under nitrogen for an additional 2 hours. During this time period, 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 °C and 2-oxazolidinone (32.77 g, 0.377 mol) was added. The mixture was heated at 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 x 100 mL), dried over anhydrous MgS04, and filtered through a pad of celite filter aid. The filtrate was concentrated under reduced pressure, then concentrated under high vacuum to give a dark oil as a crude product (150.2 g). The crude product was purified by column chromatography using a mixture of ethyl acetate / methanol gradient to give a light yellow oil (105.8 g).

[0078]

[0079] Inventive Example 3

[0080] Inventive Example 3 is commercially available 2-(phenoxy)ethyl-1-amine (Formula VII) as shown below.

[0081]

[0082] Inventive Example 4

[0083] In a 2 L 3 -necked round bottom flask, 4-nonylphenol (200.0 g, 0.908 mol) was dissolved in aromatic 100 solvent (500 mL). To this mixture was added potassium hydroxide (2.1 g), followed by hexanol (92.74 g, 0.908 mol), and the resulting mixture was stirred at room temperature under a nitrogen atmosphere using a mechanical stirrer for 30 minutes. The mixture was then heated to reflux (about 165-170 °C) and stirred under nitrogen for an additional 2 hours. During this time 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 °C and 2-oxazolidinone (102.75 g, 1.180 mol) was added. The mixture was heated at reflux and stirred under nitrogen for 18 hours (overnight). The mixture was cooled to 70 °C 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 water (500 mL) was added. The mixture was stirred for 30 minutes. The mixture was filtered and concentrated under high vacuum to yield a light yellow oil (243.67 g) as a crude product. This crude product was further washed with water (3 x 500 mL), brine (500 mL), dried over anhydrous MgS04, and filtered through a pad of celite filter aid. The filtrate was concentrated under reduced pressure, then under vacuum. The crude product was purified by column chromatography using a mixture of ethyl acetate / methanol gradient to yield a light yellow oil. (100 g) and stirred for 30 minutes. The mixture was filtered and concentrated under high vacuum to yield a light yellow oil (243.67 g) as a crude product. This crude product was further washed with water (3 x 500 mL), brine (500 mL), dried over anhydrous MgS04, and filtered through a pad of celite filter aid. The filtrate was concentrated under reduced pressure, then under vacuum. The crude product was purified by column chromatography using a mixture of ethyl acetate / methanol gradient to yield a light yellow oil.

[0084] The inventive examples were blended in gasoline and tested for their ability to mitigate DISI direct injector fouling in a test vehicle. A 2017 VW Jetta SE vehicle equipped with a 1.4L 16 valve turbocharged DISI engine was used as the test vehicle.

[0085] Figure 1 The vehicle speed conditions observed during the specified vehicle drive cycle are shown. The vehicle drive cycle is based on 10 ramps extracted from the transient phases of the Environmental Protection Agency (EPA) Urban Dynamometer Driving Schedule (UDDS), with additional idling periods added. The total drive cycle is a 20 minute duration, and the total test duration is 2,000 miles.

[0086] The additive test was conducted in a “keep clean” configuration, which starts with clean injectors and combustion chambers. This test configuration evaluates the ability of a given deposit control additive to keep the injectors and combustion chambers clean during the test duration.

[0087] Four fuel samples were subjected to injector "keep clean" testing: (i) base fuel with no addition, (ii) 200 ppmw Invention Example 1 added to sample (i), (iii) 200 ppmw Invention Example 2 added to sample (i), and (iv) 200 ppmw Invention Example 3 added to sample (i).

[0088] A set of four clean injectors was used at the start of each vehicle test. At the end of the test, photographs were taken of the four injectors of the deposits formed. Figure 2 Photographs of the injectors before and after the engine test are shown.

[0089] The flow restriction of the injectors was also measured. Table 1 shows the average injector flow restriction (%) measured at the end of the engine test compared to the base fuel reference (i.e. no added gasoline).

[0090] As shown, Invention Example 1 provided a much lower flow restriction (average 0.39%) when compared to the base fuel reference (average 2.81%). Invention Examples 2 and 3 also provided lower flow restrictions (average 1.47% and 2.15% respectively)

[0091] Injector fuel restriction measures the reduction in fuel flow from the injector, indicating the presence of deposits in the injector hole. Injector restriction can force the engine controller to make additional control adjustments to maintain proper engine fuel delivery, and the presence of deposits in the injector hole can affect fuel mixing, resulting in decreased engine performance and increased particulate emissions.

[0092] Table 1

[0093]

[0094] A second test was also performed using an engine on an engine dynamometer bench. A 2017 Honda DISI 1.5L 16 valve turbocharged engine was the test vehicle engine used. The duration of the engine drive cycle was 720 seconds, the engine speed ranged from idle to 4000 RPM, and the load varied up to 160 Nm. The total test duration was 50 hours (the test duration with base fuel of 200 ppmw Example 2 was 25 hours). Figure 3 Engine speed and load test conditions are illustrated.

[0095] A set of four clean injectors was used at the start of each engine test. At the end of the test, photographs were taken of the four injectors of the deposits formed Figure 4 ).

[0096] PM measurements were made on an engine test stand using an AVL Mini Smoke Sensor (MSS). The MSS provides a continuous, fast-response measurement of solid particulate matter and is very well correlated to gravimetric methods of traditional PM measurement.

[0097] In Figure 5 In the PM emission trace shown (for the larger 50-hour test, the 3600-second portion) it is observable how quickly PM emissions rise and fall with changes in engine conditions. To provide a useful metric for these data, reference can be made to the official measurement methods used in regulatory vehicle emissions certification (such as the US Federal Test Procedure or FTP). In these cases, the regulatory agency will simply report the aggregate total of emissions from the vehicle exhaust pipe over the course of an entire drive cycle. Applying a similar strategy to the PM data set, we integrated the PM emissions over the course of a test drive cycle. This integration was then repeated for each drive cycle and a PM emission trend line was generated over the entire test duration.

[0098] Figures 6A-6C PM emission traces are shown for the baseline fuel ( Figure 6A ), the baseline fuel with 200 ppmw of Inventive Example 1 ( Figure 6B ), and the baseline fuel with 200 ppmw of Inventive Example 2 ( Figure 6C ). The addition of 200 ppmw of Inventive Example 1 or Inventive Example 2 kept PM emissions at the same level throughout the test duration as using clean injectors at the start of the test.

[0099] All documents described herein are incorporated by reference herein to the extent that they are not inconsistent with the present disclosure, including any priority documents and / or testing procedures. As is apparent from the foregoing general description and the 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 disclosure be limited as described herein.

[0100] For the sake of brevity, certain ranges are not specifically recited in this document, but are nonetheless encompassed by the disclosure. For example, from any lower limit, a range can be recited with any upper limit, and from any upper limit, a range can be recited with any other upper limit, in the same way that from any lower limit, a range can be recited with any other lower limit. Further, each point or individual value within a range is encompassed, even if not specifically recited, between the endpoints of that range. Thus, each point or individual value can serve as its own lower limit or upper limit to combine with any other point or individual value or any other lower limit or upper limit, in order to recite a range that is not specifically recited.

[0101] Likewise, the term "comprising" is to be construed in the manner set out in the foregoing paragraphs. Likewise, the term "comprising" is to be construed as meaning "including" rather than "consisting of". Furthermore, the term "consisting of" is to be construed as meaning "including at least the elements recited" rather than "including only those elements recited".

[0102] The terms "a" and "an" and "the" as used herein are understood to encompass the plural as well as the singular.

[0103] Various terms have been defined above. If a term is used in the claims without being defined above, the term is given the broadest definition possible under the circumstances in which it is employed, as reflected in at least one printed publication or issued patent, if not more. Additionally, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not conflicting with this application and for all jurisdictions in which such incorporation is permitted.

[0104] The foregoing description of the present disclosure illustrates and describes the present disclosure. Additionally, the disclosure shows and describes only the preferred embodiments, but as aforementioned, it is to be understood that the disclosure is capable of use in various other combinations, modifications, and environments and is capable of changes or modifications within the scope of the concepts as expressed herein, commensurate with the above teachings and / or the skill or knowledge of the related art. While the foregoing relates to embodiments of the present disclosure, further and additional embodiments of the present disclosure can be devised without departing from the basic scope thereof, and that scope is determined by the claims that follow, the claims being inclusive of all equivalents.

[0105] It is to be understood that the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Pronouns in the masculine form include the feminine and neuter forms as well, and vice versa, and the singular form includes the plural form, unless the context clearly dictates otherwise.

[0106] The embodiments described above are intended to explain and describe the known best mode of practicing the present application and to enable others skilled in the art to utilize the disclosure in such or other embodiments. However, the above description is intended to be illustrative and not restrictive. For example, the above-described embodiments (and / or aspects thereof) can be used in combination with each other. Such modifications to the inventive concept are intended to be within the scope of the claims. Further, it is intended that changes be made in the general principles reported here in application, their implementations, and their details, where changes are technically feasible.

Claims

1. A fuel composition comprising: gasoline; and an aryloxyalkyl amine additive having the structure: wherein the aryloxyalkyl amine additive is present at 10 to 750 ppm by weight based on the total weight of the fuel composition; wherein X is a hydrocarbyl group having 1 or 2 carbon atoms; and wherein R 1 and R 2 are independently hydrogen or substituted hydrocarbyl groups 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 detergent.

4. The fuel composition of claim 3, wherein the nitrogen-containing detergent is an aliphatic hydrocarbyl amine, a hydrocarbyl-substituted poly(oxyalkylene) amine, a hydrocarbyl-substituted succinimide, a Mannich reaction product, a nitro and amino aromatic ester of a polyalkylphenoxyalkanol, or a polyalkylphenoxyaminoalkane.

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

6. The fuel composition of claim 1, further comprising a pour point depressant.

7. The fuel composition of claim 1, wherein the aryloxyalkyl amine 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-icosylphenoxy)ethyl-1-amine, 2-(4- docosylphenoxy)ethyl-1-amine, or 2-(4-tetracosylphenoxy)ethyl-1-amine.

8. A concentrate composition comprising: 10 to 90 weight percent of an organic solvent boiling in the range of 65 °C to 205 °C; and 10 to 100 weight percent of a fuel additive, the fuel additive comprising: an aryloxyalkyl amine given by the formula wherein X is a hydrocarbyl group having 1 or 2 carbon atoms; and wherein R 1 and R 2 are independently hydrogen or substituted hydrocarbyl groups of up to 36 carbon atoms, wherein the concentrate composition further comprises a nitrogen-containing detergent, wherein the sum of all component contents is 100 weight percent.

9. The concentrate composition of claim 8, wherein X is ethylene.

10. The concentrate composition of claim 8, wherein the nitrogen-containing detergent is an aliphatic hydrocarbyl amine, a hydrocarbyl-substituted poly(oxyalkylene) amine, a hydrocarbyl-substituted succinimide, a Mannich reaction product, a nitro and amino aromatic ester of a polyalkylphenoxyalkanol, or a polyalkylphenoxyaminoalkane.

11. The concentrate composition of claim 8, wherein R 1 and at least one of R 2 is hydrogen.

12. The concentrate composition of claim 8, wherein the aryloxyalkyl amine 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-icosylphenoxy)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: an aryloxyalkyl amine additive having the structure wherein the aryloxyalkyl amine additive is present at 10 to 750 ppm by weight based on the total weight of the gasoline composition; wherein X is a hydrocarbyl group having 1 or 2 carbon atoms; and wherein R 1 and R 2 are 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 detergent.

16. The method of claim 15, wherein the nitrogen-containing detergent is an aliphatic hydrocarbyl amine, a hydrocarbyl-substituted poly(oxyalkylene) amine, a hydrocarbyl-substituted succinimide, a Mannich reaction product, a nitro and amino aromatic ester of a polyalkylphenoxyalkanol, or a polyalkylphenoxyaminoalkane.

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

18. The method of claim 16, further comprising a pour point depressant.

19. The method of claim 13, wherein the aryloxyalkyl amine 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-icosylphenoxy)ethyl- 1 -amine, 2-(4- docosylphenoxy)ethyl- 1 -amine, or 2-(4-tetracosylphenoxy)ethyl- 1 -amine.

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