Polyetheramine salts and their use as corrosion inhibitors and friction reducers

Abstract

The present disclosure relates generally to a fuel additive composition for use in reducing corrosion and wear in an internal combustion engine or its fuel components. The fuel additive composition comprises a polyetheramine salt obtained by either (a) combining a polyoxyalkylene monoamine with at least one dicarboxylic or tricarboxylic acid, or (b) combining a polyoxyalkylene polyamine with at least one monocarboxylic, dicarboxylic, or tricarboxylic acid.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63 / 079,155, filed September 16, 2020. The above application(s) are incorporated herein by reference.

[0002] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT Not applicable.

[0003] Field The present disclosure generally relates to a fuel additive composition comprising a polyetheramine salt obtained by either (a) combining a polyoxyalkylene monoamine with at least one dicarboxylic or tricarboxylic acid, or (b) combining a polyoxyalkylene polyamine with at least one monocarboxylic, dicarboxylic, or tricarboxylic acid. The fuel additive composition may be useful as a corrosion inhibitor and friction modifier in fuel compositions containing hydrocarbon-based compositions. [Background technology]

[0004] In many countries, regulatory authorities have been strongly driven to reduce automobile emissions by lowering sulfur levels in fuels. During the process of lowering such levels, many of the aromatic and polar molecules that were added to fuels to increase their lubricity and thereby reduce wear on fuel pumps and injectors have also been removed. Therefore, without the presence of these molecules, the durability of fuel pumps and injectors is significantly reduced. Furthermore, gasoline direct injection (GDI) engines have recently been replaced by portable fuel injection (PFI) engines, and the higher pressures and temperatures encountered in such fuel delivery systems can further exacerbate engine wear problems.

[0005] Corrosion inhibitors are also often added to fuels to prevent corrosion in storage tanks, pipelines, and engines. Corrosion in storage tanks and pipeline systems is typically caused by water entrained in the fuel. In the case of gasoline-oxygenate blends, corrosion problems can also be caused by acidic impurities found in the oxygenates. While effective in reducing corrosion, these inhibitors generally do not exhibit sufficient friction-reducing properties to counteract the problems described above.

[0006] While state-of-the-art corrosion inhibitors and wear reducers may be suitable for certain applications, there is a need to develop alternative compounds that can provide both corrosion inhibition and friction reduction and that, when added to fuels at low concentrations, do not introduce undesirable side effects into the fuel systems and engines in which they are used. Summary of the Invention

[0007] The present disclosure generally provides a fuel additive composition that reduces corrosion and increases lubricity of hydrocarbon-based compositions in contact with fuel system components or internal combustion engines, the composition comprising a polyetheramine salt obtained by either (a) combining a polyoxyalkylene monoamine with at least one dicarboxylic or tricarboxylic acid, or (b) combining a polyoxyalkylene polyamine with at least one monocarboxylic, dicarboxylic, or tricarboxylic acid.

[0008] In yet another embodiment, provided is a corrosion and friction inhibiting fuel composition comprising the fuel additive composition of the present disclosure and a hydrocarbon-based composition.

[0009] In yet another embodiment, provided is a method for preventing corrosion and wear of metal, plastic, or synthetic parts or surfaces of fuel system components or internal combustion engines by combining an effective amount of the fuel additive composition with a hydrocarbon-based composition to form a fuel composition, and contacting the fuel composition with the metal, plastic, or synthetic part or surface during engine operation. [Brief explanation of the drawings]

[0010] [Figure 1] 1 illustrates the anti-corrosion properties of the inventive fuel additive composition of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure generally relates to a fuel additive composition comprising a polyetheramine salt obtained by either (a) blending a polyoxyalkylene monoamine with at least one dicarboxylic or tricarboxylic acid, or (b) blending a polyoxyalkylene polyamine with at least one monocarboxylic, dicarboxylic, or tricarboxylic acid. It has been surprisingly found that, when added to a hydrocarbon-based composition, the fuel additive composition of the present disclosure can prevent or significantly reduce the amount of corrosion formed on surfaces in contact with the hydrocarbon-based composition. Furthermore, it has been surprisingly found that, when added to a hydrocarbon-based composition, the fuel additive composition can increase the lubricity of the hydrocarbon-based composition, thereby significantly reducing wear on internal combustion engine surfaces or fuel system components that are in or have been in contact with the hydrocarbon-based composition. The multifunctional nature of the fuel additive composition of the present disclosure allows it to be used, in some embodiments, substantially free of any additional state-of-the-art corrosion inhibitors or friction modifiers.

[0012] That is, use of the fuel additive composition in a hydrocarbon-based composition during operation of an internal combustion engine can result in a significant reduction in corrosion and wear in fuel system components and around the piston walls of the combustion engine. The reduction in friction should also result in improved fuel economy. Wear and corrosion of fuel system components and combustion engines can limit their useful life and, given their expensive manufacture, can be costly. Furthermore, such corrosion and wear can result in downtime, reduced safety, and reduced reliability, and the use of the fuel additive composition can extend the life of these components and engines by reducing such corrosion and wear.

[0013] The following terms shall have the following meanings:

[0014] The term "comprising" and its derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not disclosed herein. For the avoidance of doubt, all compositions claimed herein through the use of the term "comprising" may include any additional additive, adjuvant, or compound, unless stated to the contrary. In contrast, the term "consisting essentially of," when used herein, excludes any other component, step, or procedure from any subsequent recitation unless it is essential to operability, and the term "consisting of," when used, excludes any component, step, or procedure not specifically delineated or listed. The term "or," unless otherwise stated, refers to the listed components individually as well as in any combination.

[0015] The articles "a" and "an" are used herein to refer to one or more than one (i.e., at least one) of the grammatical object of the article. By way of example, "a polyetheramine" means one polyetheramine or more than one polyetheramine. The phrases "in one embodiment," "according to one embodiment," and the like generally mean that the particular feature, structure, or characteristic that follows the phrase is included in at least one embodiment of the present disclosure and may also be included in more than one embodiment of the present disclosure. Importantly, such phrases do not necessarily refer to the same embodiment. When "may," "can," "could," or "might" are used herein to describe that a certain component or feature is included or has a certain characteristic, it does not require that the particular component or feature be included or have a certain characteristic.

[0016] The term "about," as used herein, allows for a degree of variability in values ​​or ranges, for example, the degree can be within 10%, within 5%, or within 1% of the stated value or stated range limit.

[0017] Values ​​expressed in range format should be interpreted in an open manner, not only to include the numbers specified as the limits of the range, but also to include all individual numbers or subranges subsumed within that range, as if each number and subrange were specifically written down. For example, a range such as 1 to 6 should be considered to specifically disclose subranges such as 1 to 3, 2 to 4, 3 to 6, etc., as well as the individual numbers subsumed within that range, e.g., 1, 2, 3, 4, 5, and 6. This is true regardless of the breadth of the range.

[0018] The terms "preferred" and "preferably" refer to embodiments that may offer certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or different circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the present disclosure.

[0019] The term "hydrocarbon-based composition" refers to petroleum (crude oil) or liquid fuels, such as gasoline, diesel, biodiesel, kerosene, naphtha, water emulsion fuels, ethanol-based fuels, and ether-based fuels.

[0020] The term "fuel system component," as used herein, means any accessory inserted into and connected to the fuel system of an internal combustion engine (engine), including, for example, a canister, a fuel filter, a fuel pump, etc.

[0021] The term "corrosion" refers to any deterioration, rusting, weakening, deterioration, or softening of any surface, including a storage tank, pipeline, engine surface, or fuel system component, due to contact with or combustion of a hydrocarbon-based composition.

[0022] The terms "corrosion inhibition" or "reducing corrosion" refer to any improvement in minimizing, reducing, eliminating, or preventing corrosion.

[0023] The terms "friction reduction" or "reducing friction" refer to a reduction in friction losses due to friction between a hydrocarbon-based composition and a storage tank, pipeline, engine surface, or fuel system component due to contact with or combustion of the hydrocarbon-based composition.

[0024] The term "alkyl" refers to a straight or branched saturated aliphatic hydrocarbon chain having 1 to 24 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, (1-methylethyl) ), butyl, tert-butyl (1,1-dimethylethyl), etc.

[0025] The term "alkenyl" includes unsaturated aliphatic hydrocarbon chains having 2 to 24 carbon atoms, for example, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, and the like.

[0026] The alkyl or alkenyl groups mentioned above can be substituted at their termini with a heteroatom, such as a nitrogen atom, sulfur atom, or oxygen atom, to form an aminoalkyl, oxyalkyl, or thioalkyl group, such as aminomethyl, thioethyl, oxypropyl, etc. Similarly, the alkyl or alkenyl groups mentioned above can have a heteroatom inserted into the chain, to form an alkylaminoalkyl, alkylthioalkyl, alkoxyalkyl group, such as methylaminoethyl, ethylthiopropyl, methoxymethyl, etc.

[0027] The term "alicyclic" includes any cyclic hydrocarbyl having from 3 to 8 carbon atoms. Examples of suitable alicyclic groups include cyclopropanyl, cyclobutanyl, cyclopentyl, and the like.

[0028] The term "heterocyclic" includes any cyclic hydrocarbyl having 3 to 8 carbon atoms interrupted by a heteroatom, such as a nitrogen atom, a sulfur atom, or an oxygen atom. Examples of heterocyclic groups include groups derived from tetrahydrofuran, furan, thiophene, pyrrolidine, piperidine, pyridine, pyrrole, picoline, and coumarin.

[0029] The alkyl, alkenyl, alicyclic, and heterocyclic groups can be unsubstituted or substituted, for example, with aryl, heteroaryl, C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkoxy, amino, carboxy, halo, nitro, cyano, —SOH, phosphono, or hydroxy. When the alkyl, alkenyl, alicyclic, or heterocyclic group is substituted, the substitution is preferably C1-C4 alkyl, halo, nitro, amido, hydroxy, carboxy, sulfo, or orphosphono.

[0030] The term "aryl" includes aromatic hydrocarbyls containing fused aromatic rings, and includes, for example, phenyl and naphthyl.

[0031] The term "heteroaryl" includes heterocyclic aromatic derivatives having at least one heteroatom, such as nitrogen, oxygen, phosphorus, or sulfur, and heteroaryls include, for example, furyl, pyrrolyl, thienyl, oxazolyl, pyridyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, and isothiazolyl.

[0032] The term "heteroaryl" also includes fused rings in which at least one ring is aromatic, and heteroaryls include, for example, indolyl, purinyl, and benzofuryl.

[0033] The aryl and heteroaryl groups can be ring unsubstituted or substituted, for example, with aryl, heteroaryl, alkyl, alkenyl, alkoxy, amino, carboxy, halo, nitro, cyano, -SOH, phosphono, or hydroxy. When an aryl, aralkyl, or heteroaryl is substituted, the substitution is preferably C1-C4 alkyl, halo, nitro, amido, hydroxy, carboxy, sulfo, or orphosphono.

[0034] Where substituents are designated by their conventional chemical formula and written from left to right, such substituents equally encompass the chemically identical substituents that could be obtained by writing the structure from right to left, e.g., -CHO- is equivalent to -OCH-.

[0035] The term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes both the occurrence and non-occurrence of the event or circumstance.

[0036] According to one embodiment, the polyetheramine salt of the fuel additive composition can be obtained by either (a) combining a polyoxyalkylene monoamine with at least one dicarboxylic or tricarboxylic acid, or (b) combining a polyoxyalkylene polyamine with at least one monocarboxylic, dicarboxylic, or tricarboxylic acid.

[0037] In one embodiment, the polyoxyalkylene monoamine is a compound having one amino group attached to the end of a polyether backbone. The amino group may be a primary (—NH) amino group or a secondary (—NH—) amino group. In one embodiment, the amino group is a primary amino group. As further described below, the polyether backbone is based on, or defined by, alkylene oxide groups, such as propylene oxide (PO), ethylene oxide (EO), butylene oxide (BO), and mixtures thereof. In a mixed structure, the mixing ratio can be any desired ratio, and may be arranged in blocks (e.g., repeating or alternating) or randomly dispersed. In one non-limiting example, in a mixed EO / PO structure, the EO:PO ratio can range from about 1:1 to about 1:50, and vice versa. Thus, the polyoxyalkylene monoamine can essentially be defined as polyethylene oxide, polypropylene oxide, and / or polybutylene oxide. The molecular weight of the polyoxyalkylene monoamine can vary and can range up to a molecular weight of about 6,000.

[0038] Polyoxyalkylene monoamines can generally be prepared by reacting a monovalent hydrogen initiator, such as an alcohol, with ethylene and / or propylene oxide and / or butylene oxide. Following this reaction, the resulting terminal hydroxyl groups are converted to amines, thereby yielding a polyether backbone having terminal amino groups, such as terminal primary or secondary amino groups, preferably primary amino groups, with propylene oxide (PO), ethylene oxide (EO), butylene oxide (BO), or a mixture thereof. According to one embodiment, the alcohol may be an aliphatic alcohol having 1 to 35 carbon atoms or an aromatic alcohol having 6 to 35 carbon atoms, both of which may be further substituted with moieties such as alkyl, aryl, arylalkyl, and alkaryl substituents. In another embodiment, the alcohol is an alkanol, such as a lower alkyl-derived alkanol, having 1 to 18 carbon atoms or 1 to 10 carbon atoms, including, for example, methanol, ethanol, propanol, butanol, isopropanol, sec-butanol, and the like. In another embodiment, the alcohol may be an alkylphenol, where the alkyl substituent is a straight or branched chain alkyl of 1 to 24 carbon atoms, e.g., 4 to 16 carbon atoms; an aryl-substituted phenol, including mono-, di-, and triphenylphenol; an alkaryl phenol; an arylalkyl phenol, such as tristyrylphenol; a naphthol; or an alkyl-substituted naphthol.

[0039] According to one particular embodiment, the polyoxyalkylene monoamine is a compound having the following general formula: [ka] In the formula, Z is C1-C 40 Alkyl group or C1-C 40 is an alkylphenol group; each Z' is independently hydrogen, methyl, or ethyl; and e is an integer from about 1 to about 50. Specific examples include, but are not limited to, compounds having the following formula: [ka] [ka] and [ka] wherein Me is methyl, Et is ethyl, f is an integer from about 13 to about 14, and e is an integer from about 2 to about 3. Such polyoxyalkylene monoamines within the above formula include JEFFAMINE® M-600, M-1000, M-2005, M-2070, FL-1000 (when f is 14 and Me or Et is methyl), C-300 (when e is about 2.5); XTJ-435 amine, and XTJ-436 amine.

[0040] According to another embodiment, the polyoxyalkylene polyamine is a polyoxyalkylene diamine. The preparation procedure of polyoxyalkylene diamine is described, for example, in U.S. Patent No. 3,654,370, the contents of which are incorporated herein by reference. In one particular embodiment, the polyoxyalkylene diamine is an amine-terminated polyoxyalkylene diol. Such polyoxyalkylene The polyether backbone of the diol can include ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, and thus the polyoxyalkylene primary diamine can have the general formula: [ka] wherein m is an integer from 2 to about 100, and each R2 is independently hydrogen, methyl, or ethyl. In some embodiments, each R2 is independently hydrogen or methyl, and m is an integer from 2 to about 70, or from 2 to about 35, or from 2 to about 7. In other embodiments, each R2 is independently hydrogen or methyl, and m is an integer from 6 to about 70, or from about 6 to about 35. In still further embodiments, each R2 is methyl, and m is an integer from 2 to about 70. Examples of such compounds include the JEFFAMINE® D series of amines available from Huntsman Petrochemical LLC, such as JEFFAMINE® D-230 amine, in which R2 is methyl and m is about 2.6, and JEFFAMINE® D400 amine, in which R2 is methyl and m is about 6.1, as well as similar compounds with polyoxyalkylene primary diamines from other companies.

[0041] In another embodiment, the polyoxyalkylene diamine has the general formula: [ka] wherein n and p are each independently an integer from about 1 to about 10, and o is an integer from about 2 to about 40. In some embodiments, o is an integer from about 2 to about 40, or from about 2 to about 13, or from about 2 to about 10. In other embodiments, o is an integer from about 9 to about 40, or from about 12 to about 40, or from about 15 to about 40, or even from about 25 to about 40. In other embodiments, n+p is an integer in the range of about 1 to about 6, or from about 1 to about 4, or from about 1 to about 3. In further embodiments, n+p is an integer in the range of about 2 to about 6, or from about 3 to about 6. Examples of such compounds include the JEFFAMINE® ED series of amines available from Huntsman Petrochemical LLC, as well as similar compounds with polyoxyalkylene primary diamines from other companies.

[0042] In yet another embodiment, the polyoxyalkylene diamine can have the formula: [ka] where g is an integer from about 2 to about 3. Examples of such compounds include the JEFFAMINE® EDR series of amines available from Huntsman Petrochemical LLC, as well as similar compounds with polyoxyalkylene primary diamines from other companies.

[0043] In yet another embodiment, the polyoxyalkylene polyamine is a polyoxyalkylene triamine. The polyoxyalkylene triamine can also be based on ethylene oxide, propylene oxide, or butylene oxide, as well as mixtures thereof, and can be prepared by reacting such oxides with a triol initiator (e.g., glycerin or trimethylolpropane), followed by amination of the terminal hydroxyl groups. In one embodiment, the polyoxyalkylene triamine can have the formula: [ka] wherein each R3 is independently hydrogen, methyl, or ethyl; R4 is hydrogen, methyl, or ethyl; t is 0 or 1; and h, i, and j are independently integers from about 1 to about 100. In one embodiment, R4 is hydrogen or ethyl. In another embodiment, each R3 is independently hydrogen or methyl, and in some embodiments, each R3 is methyl. In yet other embodiments, h+i+j is an integer in the range of about 1 to about 100, or in the range of about 5 to about 85. Examples of such compounds include the JJEFFAMINE® T series of amines available from Huntsman Petrochemical LLC, such as JEFFAMINE® T3000, where R3 is methyl, R4 is hydrogen, t is 0, and h+i+j is 50, as well as similar compounds with polyoxyalkylene primary triamines from other companies.

[0044] The polyetheramine salts of the present disclosure can be prepared by mixing a polyoxyalkylene monoamine or polyamine with a carboxylic acid in the perfect ratio of salt under ambient or elevated temperature with gentle agitation. The carboxylic acid can be saturated or unsaturated, with linear and / or branched chains. The carboxylic acid can be natural or synthetic, aliphatic or aromatic. The carboxylic acid can have the formula R-(COOH) n where R can be hydrogen, alkyl, alkenyl, cycloaliphatic, aryl, heteroaryl, or heterocyclic; and n is 1, 2, or 3.

[0045] In one embodiment, the carboxylic acid is a monocarboxylic acid. Preferably, the monocarboxylic acid is a C-C 24Examples of monocarboxylic acids include formic acid, acetic acid, propanoic acid, isopropanoic acid, butanoic acid, pentanoic acid, isopentanoic acid, neopentanoic acid, hexanoic acid, isohexanoic acid, 2-ethylbutanoic acid, heptanoic acid, 2-methylhexanoic acid, isoheptanoic acid, neoheptanoic acid, octanoic acid, isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, and isohexanoic acid. These include, but are not limited to, sodecanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, margaric acid, glycolic acid, lactic acid, salicylic acid, acetylsalicylic acid, stearic acid, mandelic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, nonadecanoic acid, erucic acid, behenic acid, and mixtures thereof.

[0046] According to another embodiment, the carboxylic acid is a dicarboxylic acid. Examples of dicarboxylic acids include, but are not limited to, maleic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid, dimer acids obtained from the polymerization of unsaturated fatty acids and generally having an average of about 18 to about 44 carbon atoms, and mixtures thereof.

[0047] In yet another embodiment, the carboxylic acid is a tricarboxylic acid. Examples of tricarboxylic acids include, but are not limited to, trimellitic acid, citric acid, isocitric acid, and agaicic acid, trimer acids obtained from the trimerization of unsaturated fatty acids and generally having an average of about 18 to about 30 carbon atoms, and mixtures thereof.

[0048] In addition to the polyetheramine salts discussed above, the fuel additive composition can further contain one or more additional performance-enhancing additives. These additional performance-enhancing additives can be based on several factors, including, for example, the type of internal combustion engine and the type and quality of the hydrocarbon-based composition used in the engine, as well as the operating conditions under which the engine is operated. The additional performance-enhancing additives can include organic solvents, antioxidants, such as hindered phenols or their derivatives and / or diarylamines or their derivatives, different corrosion inhibitors, such as alkenyl succinic acids, including PIB succinic acid, and / or surfactant / dispersant additives, such as Mannich base dispersants, including reaction products of hydrocarbyl-substituted phenols with aldehydes and amines or ammonia; polyisobutylene amines; or glyoxylic acid compounds.

[0049] Further additives may include dyes, bacteriostats and biocides, gum inhibitors, marking agents, and demulsifiers, such as polyalkoxylated alcohols. Other additives may include additional lubricants, such as fatty carboxylic acids, metal deactivators, such as aromatic triazoles or their derivatives, and valve seat recession additives, such as alkali metal sulfosuccinates. Additional additives may include antistatic agents, deicers, combustion improvers, such as octane or cetane improvers, and flow agents, such as mineral oils and / or poly(alpha-olefins) and / or polyethers.

[0050] The polyetheramine salt may be present in the fuel additive composition in an amount of at least 0.5 wt.%, or at least 1 wt.%, or at least 10 wt.%, or at least 20 wt.%, or at least 30 wt.%, or at least 40 wt.%, or at least 50 wt.%, or at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or even at least 99 wt.%, based on the total weight of the fuel additive composition.

[0051] In other embodiments, the one or more additional performance-enhancing additives may be present in the fuel additive composition in an amount of less than 90 wt.%, or less than 50 wt.%, or less than 20 wt.%, or less than 10 wt.%, or less than 1 wt.%, based on the total weight of the fuel additive composition.

[0052] Examples of fuel additive compositions are shown in the table below. [Table 1]

[0053] According to another embodiment, provided is a packaged product comprising: a) a container having at least an outlet; and b) a fuel additive composition.

[0054] According to one embodiment, the packaged product of the present disclosure includes a container having a closure means for sealing the container, such as a lid, cover, cap, or stopper. In another embodiment, the sealed container also has a nozzle or spout. The sealed container can have the shape of a cylinder, oval, circle, rectangle, canister, tub, square, or jug ​​and contains the fuel additive composition of the present disclosure.

[0055] In yet another embodiment, the container can be made of any material, including, for example, steel, glass, aluminum, cardboard, tin, plastic, including, but not limited to, high density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), oriented polypropylene (OPP), polyethylene (PE), or polyamide, as well as blends, laminates, or other combinations of these materials.

[0056] According to another embodiment, provided is a fuel composition comprising a fuel additive composition and a hydrocarbon-based composition.

[0057] In further embodiments, the fuel additive composition may be present in the fuel composition in an amount such that the polyetheramine salt is present in an amount of at least 10 ppm, 12 ppm, 25 ppm, 50 ppm, 100 ppm, 150 ppm, 200 ppm, or 300 ppm, based on the total weight of the fuel composition. In other embodiments, the fuel additive may be added to the fuel composition in an amount such that the polyetheramine salt is present in an amount less than 5000 ppm, 2500 ppm, 2000 ppm, 1500 ppm, 1000 ppm, 750 ppm, or 500 ppm, based on the total weight of the fuel composition.

[0058] In another embodiment, the hydrocarbon-based composition is liquid at room temperature and is useful for fueling engines. The hydrocarbon-based composition can be a petroleum fraction, including gasoline, as defined in ASTM specification D4814, and in other embodiments, the hydrocarbon-based composition is leaded or unleaded gasoline. The fuel composition can further contain oxygenates, such as alcohols, ethers, ketones, carboxylic acid esters, nitroalkanes, or the like. For example, the fuel composition may include, for example, methanol, ethanol, butanol, methyl t-butyl ether, and methyl ethyl ketone. In one embodiment, the fuel composition may include 0.1% to 100% by volume of the oxygenate, based on the total volume of the fuel composition. In yet another embodiment, the fuel composition may include 0.1% to 100% by volume of a hydrocarbon-based composition, such as gasoline, based on the total volume of the fuel composition. In yet another embodiment, the oxygenate may be ethanol. In another embodiment, the fuel composition may include gasoline and 5% to 30% by volume of ethanol, based on the total volume of the fuel composition.

[0059] The fuel composition can be prepared by mixing the hydrocarbon-based composition, the fuel additive composition, and the oxygenate before the hydrocarbon-based composition is placed in the vehicle. For example, the fuel additive composition can be added to and mixed with the hydrocarbon-based composition so that the polyetheramine salt is present at a concentration of at least 10 ppm, or at least 20 ppm, or at least 50 ppm, or at least 100 ppm, based on the total weight of the fuel composition. The additized fuel composition can then be pumped into the fuel tank. In another embodiment, the fuel composition can be added to the vehicle's fuel tank, and the fuel additive composition containing the polyetheramine salt can be added to a separate additive tank in the vehicle. This fuel additive composition can then be added to the fuel composition at a concentration of at least 10 ppm when the vehicle is running. This is known as "onboard dosing."

[0060] In one embodiment, the fuel compositions described above are useful in liquid fuel engines and / or spark ignition engines, including hybrid vehicle engines and stationary engines. The engine type is not unduly limited and includes, but is not limited to, V-engines, in-line engines, opposed engines, and rotary engines. The engine can be a naturally aspirated engine, a supercharged engine, an E-turbocharged engine, a supercharged engine, or a turbocharged engine. The engine can be a carbureted or fuel-injected gasoline engine. As such, the engine can have a carburetor or injectors (including piezoelectric injectors).

[0061] In one embodiment, the engine can be a gasoline direct injection ("GDI") engine (injected or wall-guided, or a combination thereof), a port fuel injection ("PFI") engine, a homogeneous charge compression ignition ("HCCI") engine, a stoichiometric or lean-burn engine, a spark-controlled compression ignition ("SPCCI") engine, a variable compression ratio engine, a Miller cycle engine, or an Atkinson cycle engine, or a combination thereof, such as an engine having both GDI and PFI injectors in the same engine. Suitable GDI / PFI engines include two-stroke or four-stroke engines fueled with gasoline, blended gasoline / alcohol, or any of the fuel compositions described in the preceding sections. The fuel composition can reduce corrosion, wear, and / or improve fuel economy of an engine, such as a GDI or GDI / PFI engine. In yet another embodiment, the fuel composition can be prepared using an on-board addition system for a GDI engine, a PFI engine, or a combination thereof.

[0062] In other embodiments, any of the above engines can be equipped with catalysts or devices for exhaust gas treatment, for example, NOx reduction. In other embodiments, the engine can be a flex-fuel engine, capable of running on more than one fuel, typically gasoline and ethanol or gasoline and methanol. In yet other embodiments, any of the above engine types can be in a hybrid vehicle, and this hybrid vehicle It also has an electric motor.

[0063] Thus, in another embodiment, provided is a method for preventing corrosion and wear reduction of fuel system components or metal, plastic, or synthetic parts or surfaces of an internal combustion engine by combining an effective amount of a fuel additive composition with a hydrocarbon-based composition to form a fuel composition, and contacting the fuel composition with the metal, plastic, or synthetic part or surface during operation of the engine.

[0064] Generally, the fuel additive composition can be added to a hydrocarbon-based composition or gasoline in small amounts, i.e., in an amount effective to provide corrosion reduction and friction reduction to the gasoline. The fuel additive composition may be effective in an amount ranging from about 0.0002 to 0.2 wt. %, based on the total weight of the gasoline. In some embodiments, an amount ranging from about 0.001 to 0.01 wt. %, based on the total weight of the gasoline, may be suitable, the latter amount corresponding to about 3 PTB and 30 PTB (pounds of additive per 1000 barrels of hydrocarbon fuel or gasoline), respectively.

[0065] In yet another embodiment, provided is a method for preventing corrosion and wear reduction of fuel system components or metal, plastic, or synthetic parts or surfaces of an internal combustion engine by combining an effective amount of the fuel additive composition with a hydrocarbon-based composition to form a fuel composition, and contacting the fuel composition with the metal, plastic, or synthetic parts or surfaces during operation of the engine.

[0066] It is known that, prior to combustion, certain fuel additives may reach the thin film of lubricant that coats the cylinder walls and, over time, may accumulate in engine oil. Accordingly, in one embodiment, it is contemplated that the polyetheramine salt of the fuel additive composition will accumulate in the engine oil. That is, in one embodiment, the present disclosure provides an oil composition comprising an engine oil and a polyetheramine salt of the fuel additive composition as defined herein.

[0067] The present disclosure will now be further described with reference to the following non-limiting examples. [Example]

[0068] A high frequency reciprocating rig (HFRR) was used to test the friction reduction of the fuel additive compositions of the present disclosure in gasoline. The HFRR was manufactured by PCS Group. The gasoline was purchased from Haltermann Solutions (HF0437, Tier II EEE). The liquid load volume was approximately 15 ml. The HFRR tests in gasoline were conducted under the following conditions: Duration: 75 minutes Temperature 25°C Frequency 50Hz Stroke 1mm Loading 200g Specimen: Steel AISI E-52100

[0069] To characterize corrosion inhibitor performance, carbon steel coupons were sanded with abrasive paper prior to use, and then half of the coupons were immersed in a liquid fuel composition and maintained under agitation at a temperature of about 30°C for 5 hours, as further described below.

[0070] Synthesis of fuel additive compositions Polyoxyalkylene monoamine or polyamine and carboxylic acid are mixed in a ratio of the number of amines to the number of acids. and mixed for 60 minutes at ambient temperature in an approximately 1:1 ratio. The carboxylic acids included oleic acid, isostearic acid, and dimer acid. The polyoxyalkylene monoamines and polyamines included JEFFAMINE® C-300, M-600, FL-1000, D-230, D-400, and T-3000 amines. The fuel additive compositions are summarized in the table below. [Table 2]

[0071] HFRR evaluation of fuel additive compositions at 0.15% (1500 ppm) salt addition level in gasoline. Examples 1 and 2 were blended with unadditized gasoline (HF0437) at a polyetheramine salt addition level of 1500 ppm. Wear scar was measured for each example according to ASTM D6709. The results are shown below. [Table 3]

[0072] HFRR evaluation of fuel additive compositions at 0.30% (300 ppm) salt addition level in gasoline. Examples 1, 3, 4, 5, 6, and 8 were blended with unadditized gasoline (HF0437) at a polyetheramine salt addition level of 300 ppm. For each example, wear scar was measured according to the following. The results are shown below. [Table 4]

[0073] HFRR evaluation of fuel additive compositions at 0.15% (150 ppm) salt addition level in gasoline. Examples 1, 3, 4, 5, 6, and 7 were blended with unadditized gasoline (HF0437) at a polyetheramine salt addition level of 150 ppm. Wear scars were measured for each example. The results are shown below. [Table 5]

[0074] As demonstrated above, fuel additive compositions according to the present disclosure can significantly reduce wear even at very low polyetheramine salt addition levels.

[0075] Evaluation of the rust-inhibiting performance of fuel additive compositions at 0.10% (100 ppm) salt addition level in gasoline / salt water mixtures. 150 g of HF0437 was blended with 15 g of seawater, and then the examples were added as shown below: To determine the corrosion inhibitor performance, carbon steel coupons were sanded with abrasive paper before use, and then half of the metal coupons were immersed in the liquid fuel additive and maintained under agitation at a temperature of about 30°C for 5 hours. [Table 6]

[0076] Based on the results shown in FIG. 1, the fuel additive compositions according to the present disclosure provided rust inhibitory performance in gasoline / seawater mixtures, and in particular, the fuel additive compositions of the present invention provided significantly better rust inhibitory performance than the comparative fuel additive compositions C1 and C2.

[0077] While the making and using of various embodiments of the invention have been described in detail above, it should be understood that the invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention, and do not delimit the scope of the invention.

Claims

1. 1. A fuel additive composition for reducing corrosion and increasing lubricity in a hydrocarbon-based composition in contact with a fuel system component or an internal combustion engine, comprising: Polyetheramine salts obtained by mixing polyoxyalkylene monoamines or polyoxyalkylene polyamines with carboxylic acids in the perfect ratio of salts under ambient conditions, The carboxylic acid includes any compound of the formula R-(COOH) n , where R is hydrogen, alkyl, alkenyl, cycloaliphatic, aryl, heteroaryl, or heterocyclic group, and n is 1, 2, or 3; The polyoxyalkylene monoamine is represented by the following general formula: 【Chemistry 1】 wherein Z is a C 1 -C 40 alkyl group or a C 1 -C 40 alkylphenol group; each Z′ is independently hydrogen, methyl, or ethyl; and e is an integer from about 1 to about 50; and The polyoxyalkylene polyamine has the following formula: 【Chemistry 2】 wherein m is an integer from 2 to about 100, and each R 2 is independently hydrogen, methyl, or ethyl; or a polyoxyalkylene primary diamine compound having the formula Chilentriamines have the formula: 【Transformation 3】 wherein each R 3 is independently hydrogen, methyl, or ethyl; R 4 is hydrogen, methyl, or ethyl; t is 0 or 1; and h, i, and j are independently integers from about 1 to about 100. is a compound having the formula Fuel additive compositions.

2. Each R 2 2. The fuel additive composition according to claim 1, wherein is independently hydrogen or methyl, and m is an integer from 2 to about 70.

3. 2. The fuel additive composition of claim 1, wherein the monocarboxylic acid is selected from the group consisting of formic acid, acetic acid, propanoic acid, isopropanoic acid, butanoic acid, pentanoic acid, isopentanoic acid, neopentanoic acid, hexanoic acid, isohexanoic acid, 2-ethylbutanoic acid, heptanoic acid, 2-methylhexanoic acid, isoheptanoic acid, neoheptanoic acid, octanoic acid, isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, isodecanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, margaric acid, glycolic acid, lactic acid, salicylic acid, acetylsalicylic acid, stearic acid, mandelic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, nonadecanoic acid, erucic acid, behenic acid, and mixtures thereof.

4. 2. The fuel additive composition of claim 1, wherein the carboxylic acid is a dicarboxylic acid selected from maleic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid, dimer acid, and mixtures thereof.

5. 2. The fuel additive composition according to claim 1, wherein the polyetheramine salt is obtained by mixing a polyoxyalkylene monoamine with a dicarboxylic acid.

6. 2. The fuel additive composition according to claim 1, wherein the polyetheramine salt is obtained by mixing a polyoxyalkylene diamine with a dicarboxylic acid.

7. 10. The fuel additive composition of claim 1, further comprising one or more performance enhancing additives.

8. A fuel composition comprising the fuel additive composition of claim 1 and a hydrocarbon-based composition.

9. 9. The fuel composition of claim 8, wherein the hydrocarbonaceous composition comprises gasoline.

10. 10. The fuel composition of claim 9, further comprising an oxygenate.

11. 11. The fuel composition of claim 10, wherein the oxygenate comprises ethanol.

12. 12. The fuel composition of claim 11, wherein the fuel composition comprises ethanol in an amount of 5% to 30% by volume, based on the total weight of the fuel composition.

13. 10. A method for preventing corrosion and wear of fuel system components or metal, plastic, or synthetic parts or surfaces of an internal combustion engine, comprising combining an effective amount of the fuel additive composition of claim 1 with a hydrocarbon-based composition to form a fuel composition, and contacting the fuel composition with the metal, plastic, or synthetic part or surface during operation of the engine.

14. 14. The method of claim 13, wherein the internal combustion engine is a direct injection gasoline engine.

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