Aryloxy alkylamine as fuel additive for reducing deposit in injector of direct injection spark ignition gasoline engine

Abstract

To provide a composition and a method of controlling deposit formation in a direct injection spark ignition gasoline engine.SOLUTION: The fuel composition includes gasoline and an aryloxy alkylamine additive. The structure of the aryloxy alkylamine additive is given by Formula I. In the formula, the aryloxy alkylamine additive is included in an amount of about 10 to about 750 ppm by weight based on the total weight of the fuel composition. X is a hydrocarbyl group having one or two carbon atoms. R1 and R2 are each independently hydrogen or a substituted hydrocarbyl group having up to 36 carbon atoms.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This disclosure relates to fuel additives and fuel compositions containing same. More specifically, this disclosure describes compositions and methods for controlling deposit formation in direct injection spark ignition gasoline engines. [Background technology]

[0002] Conventional fuel additives developed for port fuel injection (PFI) gasoline engines are generally not optimized to control deposit formation in the injectors of direct injection spark ignition (DISI) engines, sometimes called 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. Once directly injected, the fuel is immediately exposed to high temperatures and pressures. In this environment, combustion products can accumulate on the exterior and / or interior surfaces of the injectors and nozzles (known as injector fouling).

[0003] Deposit formation, both around the injection nozzle and within the combustion chamber, can have a significant adverse effect on one or more of fuel flow rate, injection duration, and / or spray pattern, which in turn can lead to increased emissions, increased particulate matter (PM) formation, reduced fuel economy, loss of power / performance, increased wear, and / or reduced equipment life. Summary of the Invention

[0004] In one embodiment, a fuel composition is provided that includes a gasoline and an aryloxyalkylamine additive having the following structure: [ka] wherein the aryloxyalkylamine additive is present in an amount of from 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; and R 1 and R 2are independently hydrogen or hydrocarbyl groups having up to 36 carbon atoms.

[0005] In another embodiment, there is provided a concentrate composition comprising about 0 to 90 wt. % of an organic solvent boiling in the range of 65° C. to 205° C. and about 10 to 100 wt. % of a fuel additive comprising an aryloxyalkylamine having the formula: [ka] where X is a hydrocarbyl group having 1 or 2 carbon atoms, and R 1 and R 2 are independently hydrogen or a substituted hydrocarbyl group having up to 36 carbon atoms.

[0006] In yet another aspect, there is provided a method for reducing injector deposits in a direct injection spark ignition gasoline engine, comprising providing a gasoline composition containing an aryloxyalkylamine additive having the structure: [ka] wherein the aryloxyalkylamine additive is present in an amount of from 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; and R 1 and R 2 are independently hydrogen or substituted alkyl or alkenyl groups having up to 36 carbon atoms. [Brief explanation of the drawings]

[0007] [Figure 1] Graphs described in the Examples are shown. [Figure 2] Photographs described in the examples are shown. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention describes compositions and methods for deposit control in direct injection engines. More specifically, the present invention provides detergent additive compositions that can be utilized as components of fuel compositions and methods of using the compositions.

[0009] 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 include a secondary fuel additive.

[0010] hydrocarbon fuel Hydrocarbon-based fuels include gasoline and diesel.

[0011] Gasoline fuel is at least primarily C4-C 12 In one embodiment, the gasoline or gasoline boiling range components further comprise at least primarily C4-C 12 Gasoline is defined to refer to a composition comprising hydrocarbons and further having a boiling point range of about 37.8°C (100°F) to about 204°C (400°F). In an alternative embodiment, gasoline is at least primarily C4-C 12 It is defined to refer to a composition containing hydrocarbons and having a boiling point range of about 37.8°C (100°F) to about 204°C (400°F), and further defined to meet ASTM D4814.

[0012] Diesel fuel is at least primarily C 10 -C 25 Diesel refers to a middle distillate fuel containing hydrocarbons. In one embodiment, diesel further comprises at least primarily C 10 -C 25 Diesel is defined to refer to a composition comprising hydrocarbons and further having a boiling point range of about 165.6°C (330°F) to about 371.1°C (700°F). In an alternative embodiment, diesel is defined to refer to a composition comprising at least primarily C as described above. 10 -C 25It is defined to refer to a composition containing hydrocarbons and having a boiling point range of about 165.6°C (330°F) to about 371.1°C (700°F), and further defined to meet ASTM D975.

[0013] The hydrocarbon-based fuel comprises a major weight percent of the total fuel composition, hi some embodiments, the hydrocarbon-based fuel comprises about 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 95% or more, or any range from about 50% to less than 100% by weight.

[0014] According to some embodiments, the gasoline used in the present invention may be clean-burning gasoline (CBG). CBG refers to a gasoline blend that contains reduced levels of sulfur, aromatics, and olefins. The exact blend may vary depending on local regulatory definitions.

[0015] Fuel-soluble, nonvolatile 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 medium that substantially increases the nonvolatile residue (NVR), or solvent-free liquid fraction, of the fuel additive composition without significantly increasing the octane requirement. The carrier fluid may be natural or synthetic, such as mineral oil, refined petroleum, synthetic polyalkanes and alkenes, including hydrogenated and unhydrogenated polyalphaolefins, and oils derived from synthetic polyoxyalkylenes, such as those described in U.S. Patent Nos. 3,756,793, 4,191,537, and 5,004,478, and European Patent Publication Nos. 356,726 and 382,159.

[0016] The carrier fluid may 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 may be present in an amount ranging from 20 to 60% by weight (e.g., 30 to 50% by weight).

[0017] Aryloxyalkylamine fuel additives The aryloxyalkylamine fuel additive of the present invention reduces injector deposits in direct injection spark ignition gasoline engines. The additive is a nitrogen-containing detergent having the formula: [ka] In the formula, R 1 and R 2 are independently hydrogen or a hydrocarbyl group having up to 36 carbon atoms. 2 can be located in the ortho or meta position relative 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 It may be preferred that one of is a hydrocarbyl group and the other is hydrogen.

[0018] In some embodiments, the hydrocarbyl group is an alkyl group or an alkenyl group. Alkyl groups refer to saturated hydrocarbyl groups, which may be linear, branched, cyclic, or combinations of cyclic, linear, and / or branched. Alkenyl groups refer to unsaturated hydrocarbyl groups, which may be linear, branched, cyclic, or combinations of cyclic, linear, and / or branched.

[0019] 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-eicosanylphenoxy)ethyl-1-amine, 2-(4-docosanylphenoxy)ethyl-1-amine, 2-(4-tetracosanylphenoxy)ethyl-1-amine.

[0020] Said aryloxyalkylamine can be commercially available or can be obtained by any known corresponding synthetic method.For example, aryloxyalkylamine can be obtained by reacting the salt of alkylphenol with chloroacetaldehyde.Then, the obtained product is reacted with amino alcohol, and then hydrogenated in the presence of nickel catalyst to produce aryloxyalkylamine.More detailed description of aryloxyalkylamine synthesis can be found in U.S. Patent No. 3,954,872, which is incorporated herein by reference.

[0021] synthesis In general, the fuel additives of the present invention can be synthesized by any known corresponding method. A description of two known synthesis methods is provided herein.

[0022] In the first method (Method A), an alkylphenol is first reacted with a base (e.g., potassium hydroxide) to form the alkylphenoxide described above, which is further reacted with a 2-oxazolidinone under reflux conditions in an aromatic solvent to give the corresponding aminoethylated product. [ka]

[0023] In the second method (Method B), an alkylphenol is similarly first reacted with a base (e.g., potassium hydroxide) to form an alkylphenoxide, which is further reacted with a 2-oxazolidinone generated in situ from the reaction of ethanolamine with diethyl carbonate in an aromatic solvent under reflux conditions to give the corresponding aminoethylated product. [ka]

[0024] For illustrative purposes, the following example of Method B is provided.

[0025] A 1000 mL two-neck round-bottom flask was charged with a mixture of 4-eicosanylphenol, 4-docosanylphenol, 4-tetracosanylphenol, 2-eicosanylphenol, 2-docosanylphenol, and 2-tetracosanylphenol (120 g, 0.298 mol, 1.00 equiv.) with an average molecular weight of 402.71 g / mol, KOH (2.96 g, 0.0447 mol, 0.150 equiv., 85% active), and 150 mL of Aromatic 100 solvent. The flask was equipped with a mechanical stirrer, Dean-Stark trap, and reflux condenser, and the reaction mixture was refluxed for 1 hour with vigorously stirring and a nitrogen purge to remove water. The reaction mixture was cooled to approximately 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, in that order. The reaction mixture was then warmed to 120°C under a gentle N2 flow until the theoretical amount of ethanol had evolved from the reaction, after which it was warmed to 175°C with vigorous stirring under a gentle N2 flow 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 MgSO4, filtered, and concentrated to give the crude product as an amber oil (128.0 g), which was analyzed by NMR spectroscopy and HPLC.

[0026] Secondary Fuel Additives The fuel compositions of the present invention contain one or more secondary fuel additives, which are nitrogen-containing detergents that provide enhanced detergency when combined with the primary fuel additives of the present invention.

[0027] Suitable secondary fuel additives can be classified as aliphatic hydrocarbyl-substituted amines, hydrocarbyl-substituted poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides, Mannich reaction products, polyalkylphenoxyaminoalkanes, nitro- and amino-aromatic esters of polyalkylphenoxyalkanols, and nitrogen-containing carburetor / injector detergents. Each class of secondary fuel additive is described in more detail herein.

[0028] In particular, the aliphatic hydrocarbyl-substituted amines used in the present invention may 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 polyisobutenylamine and polyisobutylamine. These amines may be produced as monoamines or polyamines. The preparation of aliphatic amines is generally known and is 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 these patents are incorporated herein by reference.

[0029] In particular, the hydrocarbyl-substituted poly(oxyalkylene)amines (also referred to as "polyetheramines") used in the present invention can include hydrocarbyl poly(oxyalkylene)amines (monoamines or polyamines) in which 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 a terminal amino nitrogen atom. The oxyalkylene moiety can be oxypropylene or oxybutylene or a mixture thereof. Hydrocarbyl-substituted poly(oxyalkylene)amines are described in U.S. Pat. Nos. 6,217,624 and 5,112,364, which are incorporated herein by reference. Specific examples of hydrocarbyl-substituted poly(oxyalkylene)monoamines include alkylphenyl poly(oxyalkylene) monoamines in which the poly(oxyalkylene) moiety contains oxypropylene or oxybutylene units or a mixture of oxypropylene and oxybutylene units. The alkyl group of the alkylphenyl moiety is a straight or branched chain alkyl of from about 1 to about 24 carbon atoms. A preferred alkylphenyl moiety is tetrapropenylphenyl, where the alkyl group is a branched chain alkyl of 12 carbon atoms derived from propylene tetramer.

[0030] More specifically, 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 incorporated herein by reference. These hydrocarbyl-substituted 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. Preferred aminocarbamates are alkylphenyl poly(oxybutylene) aminocarbamates in which the amine moiety is derived from ethylenediamine or diethylenetriamine.

[0031] In particular, hydrocarbyl-substituted succinimides useful in the present invention include polyalkyl and polyalkenyl succinimides in which 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 attached to the amine nitrogen atom. Preferred hydrocarbyl-substituted succinimides include polyisobutenyl and polyisobutanyl succinimides and their derivatives. 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, as well as British Patent No. 1,486,144. All of these patents are incorporated herein by reference.

[0032] In particular, the Mannich reaction products used in the present invention typically include products obtained from the Mannich condensation of a high molecular weight alkyl-substituted hydroxyaromatic compound, an amine containing at least one reactive hydrogen, and an aldehyde. The high molecular weight alkyl-substituted hydroxyaromatic compound is preferably a polyalkylphenol, such as polypropylphenol or polybutylphenol, particularly polyisobutylphenol, where the polyalkyl group has an average molecular weight of about 600 to 3,000. The amine reactant is typically a polyamine, such as an alkylene polyamine, particularly an ethylene or polyethylene polyamine, such as ethylenediamine, diethylenetriamine, or triethylenetetramine. The aldehyde reactant is generally an aliphatic aldehyde, such as formaldehyde, including paraformaldehyde and formalin, and acetaldehyde. A preferred Mannich reaction product is obtained by condensing polyisobutylphenol with formaldehyde and diethylenetriamine, where 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 US Pat. Nos. 4,231,759 and 5,697,988, the disclosures of each of which are incorporated herein by reference.

[0033] A further class of detergent additives suitable for use in the present invention are the polyalkylphenoxyaminoalkanes. Preferred polyalkylphenoxyaminoalkanes include those having the following formula: [ka] wherein 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 amino, N-alkylamino having about 1 to about 20 carbon atoms in the alkyl group, N,N-dialkylamino 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 polyalkylphenoxyaminoalkanes of Formula II above and their preparation are described in detail in U.S. Pat. No. 5,669,939, incorporated herein by reference.

[0034] Certain detergent mixtures may be particularly useful as secondary additives in accordance with the present invention.

[0035] In some embodiments, mixtures of polyalkylphenoxyaminoalkanes and poly(oxyalkylene)amines may be used, as described in detail in U.S. Patent No. 5,851,242, which is incorporated herein by reference.

[0036] In some embodiments, mixtures of nitro and amino aromatic esters of polyalkylphenoxyalkanols may be used. Preferred nitro and amino aromatic esters of polyalkylphenoxyalkanols include those having the following formula: [ka] wherein R8 is nitro or -(CH2)-NR 13 R 14 and R 13 and R 14 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms, and R is hydrogen, hydroxy, nitro, or -NR 15 R 16 and R 15 and R 16 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms, and R 10and R 11 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms, and R 12 is a polyalkyl group having an average molecular weight in the range of about 450 to 5,000. The aromatic esters of polyalkylphenoxyalkanols shown in Formula III above and their preparation are described in detail in U.S. Pat. No. 5,618,320, which is incorporated herein by reference.

[0037] Mixtures of nitro and amino aromatic esters of polyalkylphenoxyalkanols and hydrocarbyl-substituted poly(oxyalkylene)amines can also be used in the present invention. These mixtures are described in detail in U.S. Patent No. 5,749,929, which is incorporated herein by reference. Preferred hydrocarbyl-substituted poly(oxyalkylene)amines that can be used as detergent additives in the present invention include those having the formula: [ka] In the formula, R 17 is a hydrocarbyl group having from about 1 to about 30 carbon atoms, and 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 independently, each -O-CHR 18 -CHR 19-units, m is from about 5 to about 100, B is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl group, N,N-dialkylamino 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 hydrocarbyl-substituted poly(oxyalkylene)amines of Formula IV above and their preparation are described in detail in U.S. Pat. No. 6,217,624, incorporated herein by reference. The hydrocarbyl-substituted poly(oxyalkylene)amines of Formula IV are preferably utilized by themselves or in combination with other detergent additives, particularly polyalkylphenoxyaminoalkanes or nitro- and amino-aromatic esters of polyalkylphenoxyalkanols. More preferably, the detergent additive used in the present invention is a combination of a hydrocarbyl-substituted poly(oxyalkylene)amine and a nitro- and amino-aromatic ester of a polyalkylphenoxyalkanol. A particularly preferred hydrocarbyl-substituted poly(oxyalkylene) amine detergent additive is dodecylphenoxypoly(oxybutylene)amine, and a particularly preferred detergent additive combination is dodecylphenoxypoly(oxybutylene)amine in combination with 4-polyisobutylphenoxyethyl para-aminobenzoate.

[0038] Another class of detergent additives suitable for use in the present invention includes nitrogen-containing carburetor / injector detergent additives. These carburetor / injector detergent additives are typically low molecular weight compounds having a number average molecular weight of about 100 to about 600 and containing at least one polar moiety and at least one non-polar moiety. The non-polar moiety is typically a straight- or branched-chain 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., those described in U.S. Pat. No. 5,139,534 and PCT International Publication No. WO 90 / 10051), ether amines (e.g., those described in U.S. Pat. No. 3,849,083 and PCT International Publication No. WO 90 / 10051), amides, polyamides and amide esters (e.g., those described in U.S. Pat. Nos. 2,622,018, 4,729,769, and 5,139,534, and European Patent Publication No. 149,486), imidazolines (e.g., those described in U.S. Pat. No. 4,518,782), amine oxides (e.g., those described in U.S. Pat. Nos. 4,810,263 and 4,836,829), hydroxyamines (e.g., those described in U.S. Pat. No. 4,409,000), and succinimides (e.g., those described in U.S. Pat. No. 4,292,046). Each of these references is incorporated herein by reference.

[0039] Each secondary fuel additive may be present in an amount of from 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 secondary fuel additive is present in an amount of from about 50 ppm to about 1000 ppm by weight of the fuel composition.

[0040] Other additives The fuel composition may also contain other commonly known fuel additives. Suitable examples include, but are not limited to, antioxidants, metal deactivators, demulsifiers, oxygenates, antiknock agents, dispersants, and other detergents. In diesel fuels, other well-known additives such as pour point depressants and flow improvers may be used.

[0041] Each of the foregoing additives, when used, is used in a functionally effective amount to impart the desired properties to the fuel composition. Generally, the concentration of each of these additives, when used, can range from about 0.001 to about 20 wt. %, for example, from about 0.01 to about 10 wt. %, unless otherwise specified.

[0042] concentrate The compounds of the present disclosure can be formulated as concentrates using inert, stable, lipophilic (i.e., soluble in hydrocarbon fuel) organic solvents boiling in the range of 65°C to 205°C. Aliphatic or aromatic hydrocarbon solvents, such as benzene, toluene, xylene, or higher-boiling aromatic compounds or solvents, can be used. In combination with the hydrocarbon solvent, aliphatic alcohols containing 2 to 8 carbon atoms, such as ethanol, isopropanol, methyl isobutyl carbinol, n-butanol, and the like, are also suitable for use with the additive. In the concentrate, the amount of the additive can range from 10 to 70% by weight (e.g., 20 to 40% by weight).

[0043] The following examples are intended to be non-limiting. [Example]

[0044] Example 1 Example 1 is 2-(4-dodecylphenoxy)ethyl-1-amine (Formula V) shown below.

[0045] 4-Dodecylphenol (200.0 g, 0.76 mol) was dissolved in 1000 mL of naphtha (Aromatic 100) solvent in a 2 L three-neck round-bottom flask. To this mixture, potassium hydroxide (4.3 g) was added, followed by hexanol (78 g, 0.76 mol). The resulting mixture was stirred under a nitrogen atmosphere at room temperature for 30 minutes using a mechanical stirrer. The mixture was then heated to reflux (approximately 165-170 °C) and stirred for an additional 2 hours under nitrogen. During this time, the distillate (e.g., water / hexanol and aromatic solvent) was collected in a Dean-Stark trap. After stirring for 2 hours, the mixture was cooled to 120 °C, and 2-oxazolidinone (66.0 g, 0.76 mol) was added. The mixture was heated to reflux and stirred under nitrogen for 18 hours (overnight). The mixture was cooled to room temperature, diluted with hexanes (100 mL), and the organic phase was washed with water (200 mL), brine (4 x 100 mL), dried over anhydrous MgSO4, and filtered through a pad of Celite filter aid. The filtrate was concentrated under reduced pressure and then high vacuum to give an amber oil as the crude product (240 g). [ka]

[0046] Example 2 Example 2 is a mixture of 2-(4-eicosanylphenoxy)ethyl-1-amine, 2-(4-docosanylphenoxy)ethyl-1-amine, and 2-(4-tetracosanylphenoxy)ethyl-1-amine (Formula VI), shown below, which was obtained by Method A below.

[0047] A mixture of 4-eicosanylphenol, 4-docosanylphenol, 4-tetracosanylphenol, 2-eicosanylphenol, 2-docosanylphenol, and 2-tetracosanylphenol (151.71 g, 0.377 mol) with an average molecular weight of 402.71 g / mol was dissolved in Aromatic 100 solvent (700 mL) in a 2 L three-neck round-bottom flask. To this mixture, potassium hydroxide (2.1 g) was added, followed by hexanol (38.5 g, 0.377 mol). The resulting mixture was stirred under a nitrogen atmosphere at room temperature for 30 minutes using a mechanical stirrer. The mixture was then heated to reflux (approximately 165-170 °C) and stirred for an additional 2 hours under nitrogen. During this time, the distillate (e.g., water, hexanol, and aromatic solvent) was collected in a Dean-Stark trap. 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 to reflux and stirred under nitrogen for 18 hours (overnight). The mixture was cooled to room temperature and diluted with hexane (200 mL). The organic phase was washed with water (200 mL), brine (4 x 100 mL), dried over anhydrous MgSO4, and filtered through a pad of Celite filter aid. The filtrate was concentrated under reduced pressure and then high vacuum to give a dark oil as the crude product (150.2 g). 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). [ka]

[0048] Example 3 Example 3 is commercially available 2-(phenoxy)ethyl-1-amine (Formula VII) shown below. [ka]

[0049] Example 4 4-Nonylphenol (200.0 g, 0.908 mol) was dissolved in Aromatic 100 solvent (500 mL) in a 2 L three-neck round-bottom flask. To this mixture, potassium hydroxide (2.1 g) was added, followed by hexanol (92.74 g, 0.908 mol). The resulting mixture was stirred under a nitrogen atmosphere at room temperature for 30 minutes using a mechanical stirrer. The mixture was then heated to reflux (approximately 165-170 °C) and stirred for an additional 2 hours under nitrogen. During this time, the distillate (e.g., water / hexanol and aromatic solvent) was collected in a Dean-Stark trap. 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 to reflux and stirred under nitrogen for 18 hours (overnight). The mixture was cooled to 70°C, ethylenediamine (10.91 g, 0.182 mol) was added, and the mixture was heated to reflux for 4 hours. The mixture was cooled to room temperature, and Magnesol® (100 g) was added and stirred for 30 minutes. The mixture was filtered and concentrated under high vacuum to give a light yellow oil as crude product (243.67 g). The crude product was further washed with water (3 x 500 mL), brine (500 mL), dried over anhydrous MgSO4, and filtered through a pad of Celite filter aid. The filtrate was concentrated under reduced pressure and then under high vacuum. The crude product was purified by column chromatography using a gradient of ethyl acetate / methanol mixture to give a pale yellow oil.

[0050] These examples were blended into gasoline and tested for their ability to reduce deposits in a DISI direct injection system in a test vehicle, a 2017 VW Jetta SE equipped with a 1.4L 16-valve turbocharged DISI engine.

[0051] Figure 1 shows the vehicle speed conditions observed during a specified vehicle drive cycle. The vehicle drive cycle was based on 10 ramps extracted from the transition phase of the Environmental Protection Agency's (EPA) Urban Dynamometer Driving Schedule (UDDS), with an additional idle period added. The total drive cycle was 20 minutes in duration, with a total test period of 2,000 miles.

[0052] Additive testing is performed in a "keep it clean" configuration, starting 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 over the test period.

[0053] Injector "stay clean" testing was performed on four fuel samples: (i) base fuel with no additives, (ii) sample (i) spiked with 200 ppmw of Example 1, (iii) sample (i) spiked with 200 ppmw of Example 2, and (iv) sample (i) spiked with 200 ppmw of Example 3.

[0054] 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 deposits that had formed on these four injectors. Figure 2 shows photographs of the injectors before and after the engine test.

[0055] Injector flow restriction 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., unadditized gasoline).

[0056] As shown, Example 1 exhibited much lower flow restriction (average 0.39%) compared to the base fuel reference (average 2.81%). Examples 2 and 3 also exhibited lower flow restriction (average 1.47% and 2.15%, respectively).

[0057] Injector fuel restriction measures a reduction in fuel flow from the injector and indicates the presence of deposits in the injector orifice. Injector restriction can force engine controllers to make additional control adjustments to maintain adequate engine fuel delivery, and the presence of deposits in the injector orifice can affect fuel mixing, leading to reduced engine performance and increased particulate emissions. [Table 1]

[0058] A second test was also conducted with the engine mounted on a dynamometer stand. A 2017 Honda DISI 1.5L 16-valve turbocharged engine was the test vehicle engine used. The engine drive cycle was 720 seconds in duration, with engine speed ranging from idle to 4000 RPM and load varying up to 160 Nm. The total test duration was 50 hours (the test duration for the base fuel containing 200 ppmw Example 2 was 25 hours). Figure 3 shows the engine speed and load test conditions.

[0059] A set of four clean injectors was used at the start of each engine test, and at the end of the test, photographs (Figure 4) of the deposits formed on these four injectors were taken.

[0060] PM measurements were made on an engine test stand using an AVL Micro Soot Sensor (MSS), which provides a continuous, fast-response measurement of solid particle mass and correlates well with conventional gravimetric PM measurements.

[0061] In the PM emissions trace shown in Figure 5 (a 3600-second segment of a longer 50-hour test), we can observe how quickly PM emissions increase and decrease as engine conditions change. To provide a useful metric for these data, we can look to the official measurement methods used in regulatory vehicle emissions certification (e.g., the Federal Test and Inspection Procedure, or FTP). In these cases, regulatory agencies simply publish the total amount of emissions from a vehicle's tailpipe over the entire driving cycle. A similar strategy is applied to this PM dataset to integrate PM emissions over the course of one test driving cycle. This integration is then repeated for each driving cycle, resulting in a trend line for PM emissions over the entire test period.

[0062] 6A-6C show PM emission traces from the base fuel (FIG. 6A), the base fuel with 200 ppmw of Example 1 (FIG. 6B), and the base fuel with 200 ppmw of Example 2 (FIG. 6C). The addition of Example 1 or Example 2 at 200 ppmw maintains PM emissions at the same level as at the start of the test with clean injectors for the entire duration of the test.

[0063] All documents described herein are incorporated herein by reference, including any priority documents and / or test procedures, unless inconsistent with the text. As is apparent from the foregoing general description and specific embodiments, while forms of the present disclosure have been illustrated and described, various changes can be made without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited thereby.

[0064] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to enumerate a range that is not explicitly recited, and similarly, a range from any lower limit may be combined with any other lower limit to enumerate a range that is not explicitly recited, and similarly, a range from any upper limit may be combined with any other upper limit to enumerate a range that is not explicitly recited. Furthermore, a range includes all points or individual values ​​between its endpoints, even if not explicitly recited. Thus, every point or individual value can serve as a unique lower or upper limit in combination with any other point or individual value or any other lower or upper limit to enumerate a range that is not explicitly recited.

[0065] Similarly, the term "comprising" is considered synonymous with the term "including." Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that the same composition or group of elements having the transitional phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "is" preceding the composition or list of element(s) is also contemplated, and vice versa.

[0066] As used herein, the terms "a" and "the" are understood to encompass the plural as well as the singular.

[0067] Various terms are defined above. Unless a term used in the claims is defined above, it should be given the broadest definition given to that term by one skilled in the relevant art, as found in at least one publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are incorporated by reference in their entirety to the extent such disclosure is not inconsistent with this application and for all jurisdictions where such incorporation is permitted.

[0068] The foregoing description of the present disclosure illustrates and describes the present disclosure. Moreover, while the present disclosure has shown and described only preferred embodiments, it will be understood, as noted above, that the present disclosure is capable of use in various other combinations, modifications, and environments, and that changes or modifications can be made within the scope of the concepts 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 present disclosure may be devised without departing from the basic scope thereof, which scope is determined by the following claims.

[0069] Where combinations, subsets, groups, etc. of elements (e.g., combinations of components in a composition or combinations of steps in a method) are disclosed, it is understood that specific reference to each of the various individual and collective combinations and permutations of those elements is specifically contemplated and described herein, even though it may not be explicitly disclosed.

[0070] The embodiments described herein are further intended to explain the best mode known for carrying out the present disclosure and to enable others skilled in the art to utilize the present disclosure in such or other embodiments, with various modifications as required for a particular application or use. Therefore, the present disclosure is not intended to limit the present disclosure to the forms disclosed herein. Also, 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 following structure: 【Chemistry 1】 wherein the aryloxyalkylamine additive is present in an amount of from 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.

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

3. 10. The fuel composition of claim 1, further comprising a nitrogen-containing detergent.

4. 4. The fuel composition according to 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. 10. The fuel composition of claim 1, further comprising an antioxidant, a metal deactivator, a demulsifier, an oxygenate, an anti-knock agent, a dispersant, a pour point depressant, or a flow improver.

6. 2. 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-eicosanylphenoxy)ethyl-1-amine, 2-(4-docosanylphenoxy)ethyl-1-amine, or 2-(4-tetracosanylphenoxy)ethyl-1-amine.

7. A concentrated composition comprising: about 10 to 90% by weight of an organic solvent boiling in the range of 65°C to 205°C, and About 10-100% by weight of a fuel additive comprising: formula 【Chemistry 2】 an aryloxyalkylamine given by wherein 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.

8. 8. The concentrated composition of claim 7, wherein X is an ethylene group.

9. 8. The concentrated composition of claim 7, further comprising a nitrogen-containing detergent.

10. 10. The concentrate composition of claim 9, 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. R １ and R ２ 8. The concentrated composition of claim 7, wherein at least one of is hydrogen.

12. 8. The concentrated 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-eicosanylphenoxy)ethyl-1-amine, 2-(4-docosanylphenoxy)ethyl-1-amine, or 2-(4-tetracosanylphenoxy)ethyl-1-amine.

13. 1. A method for reducing injector deposits in a direct injection spark ignition gasoline engine, comprising: providing a gasoline composition comprising: An aryloxyalkylamine additive having the structure 【Transformation 3】 wherein the aryloxyalkylamine additive is present in an amount of from 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 substituted alkyl or alkenyl groups having up to 36 carbon atoms.

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

15. The method of claim 13 further comprising a nitrogen-containing cleaning agent.

16. 14. The method of claim 13, 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. 17. The method of claim 16, further comprising an antioxidant, a metal deactivator, a demulsifier, an oxygenate, an anti-knock agent, a dispersant, a pour point depressant, or a flow improver.

18. 14. 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-eicosanylphenoxy)ethyl-1-amine, 2-(4-docosanylphenoxy)ethyl-1-amine, or 2-(4-tetracosanylphenoxy)ethyl-1-amine.

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