Fuel additives and formulations for improving gasoline direct injection engine performance

Abstract

The present invention relates to a fuel additive composition having at least one acylated detergent, at least one Mannich detergent, and at least one polyether and / or polyether amine. The acylated detergent can be a reaction product of a hydrocarbyl-substituted acylating agent and a nitrogen-containing compound having at least one amino group that is optionally quaternized and at least one oxygen or nitrogen atom capable of reacting with the hydrocarbyl-substituted acylating agent. The composition can be used to reduce the formation of carbonaceous deposits in an engine, such as a gasoline direct injection engine, and / or to clean carbonaceous deposits.

Description

Technical Field

[0001] The disclosed technical field relates in general to fuel additive compositions having at least one acylated detergent, at least one Mannich detergent, and at least one polyether and / or polyetheramine. Background Technology

[0002] In gasoline direct injection (“GDI”) engines, highly atomized fuel mist is injected directly into the combustion chamber of each engine cylinder at high pressure (typically between 450 psi and 3,000 psi). Compared to conventional port fuel injection (“PFI”) gasoline engines, where fuel is directed to the cylinder intake ports, GDI engines offer increased fuel efficiency and higher power output by injecting fuel directly into the combustion chamber. This has led to the rapid adoption of GDI engines in the automotive industry.

[0003] Because the fuel injectors are located close to the combustion chamber, GDI engines are prone to carbon buildup or "deposits" in their injectors. These deposits can affect the fuel injection pattern through the injector nozzles and reduce the amount of fuel entering the combustion chamber.

[0004] Currently, most gasoline additives on the market are designed to maintain and / or improve PFI performance. These PFI additives include detergents, such as Mannich compounds and polyetheramines, which are added to gasoline fuel to help keep the injectors clean (“keep clean”) or remove deposits build-up in the injectors and elsewhere in the engine (“clean”).

[0005] These PFI additives may not provide sufficient cleaning or removal performance in GDI vehicles, therefore, new additives are needed to provide this performance. Furthermore, tests have shown that GDI engines emit significantly more fine particulate matter in their emissions compared to PFI engines. New legislation has been introduced in Europe to regulate particulate numbers in passenger vehicles to below 6 × 10⁻⁶. 11 / km. Similar emission standards are expected to be introduced in other regions (including the United States). In response to European standards, automakers are planning to install gasoline particulate filters, but these filters are expensive, not very effective at removing very small particles, may interfere with vehicle handling, and require repair or replacement when they become clogged. Summary of the Invention

[0006] Novel fuel additive compositions have been found to be surprisingly effective in reducing deposits in port fuel injection (“PFI”) and gas direct injection (“GDI”) engines. The compositions contain acylated detergents, Mannich detergents, and polyethers and / or polyether amines.

[0007] Acylated detergents can be reaction products of hydrocarbon-substituted acylated agents and nitrogen-containing compounds having at least one quaternized amino group and at least one oxygen or nitrogen atom capable of reacting with the hydrocarbon-substituted acylated agent.

[0008] In some embodiments, at least one hydrocarbon substituent of the acylation agent may be C 16 To C 100 hydrocarbon group or C 18 To C 50 Hydrocarbon groups, such as, but not limited to, octadecene groups and / or polyisobutylene groups. In some embodiments, the hydrocarbon-substituted acylation agent may be hydrocarbon-substituted succinic acid and / or hydrocarbon-substituted succinic anhydride. Based on the total weight of the composition, the acylated detergent may be present in the composition at 5% to 50% by weight, or 10% to 45% by weight.

[0009] Mannich detergents can be reaction products of polyolefins, aldehydes, and optionally quaternized ammonia or amines. In some embodiments, the polyolefin used to prepare Mannich is polyisobutylene. Based on the total weight of the composition, Mannich detergents may be present in the composition at 20% to 80% by weight, or 30% to 70% by weight.

[0010] In some embodiments, the acylated detergent and / or Mannich detergent may be quaternized. Suitable quaternizing agents may include, but are not limited to, dialkyl sulfates, alkyl halides, hydrocarbon-substituted carbonates, carboxylic acid esters, alkyl esters, hydrocarbon epoxides, combinations of hydrocarbon epoxides and acids, or mixtures thereof. In some embodiments, only the acylated detergent is quaternized. In other embodiments, both the acylated detergent and the Mannich detergent are quaternized.

[0011] There are no excessive limitations on suitable polyethers (PE) and / or polyetheramines (PEA), and any polyether or polyetheramine with detergent properties can be present in the composition at 10% to 60% by weight or 20% to 50% by weight, based on the total weight of the composition.

[0012] In some embodiments, the composition may comprise an acylated detergent, which is the reaction product of a hydrocarbon-substituted acylated agent and a nitrogen-containing compound, wherein the hydrocarbon substituent of the acylated agent is C. 16 To C 100 Or C 18 To C 50The nitrogen-containing compound has at least one quaternized amino group and at least one oxygen or nitrogen atom capable of reacting with an acylated agent that substituted the hydrocarbon group. In some embodiments, the acylated detergent can be quaternized with a quaternizing agent comprising at least one dialkyl sulfate, alkyl halide, hydrocarbon-substituted carbonate, carboxylic acid ester, alkyl ester, hydrocarbon epoxide, a combination of hydrocarbon epoxide and an acid, or a mixture thereof.

[0013] Any of the above compositions can be used in fuel to reduce the formation of carbonaceous deposits in gasoline engines, such as gasoline port fuel injection engines or gasoline direct injection engines. In some embodiments, the composition is used in fuel to reduce deposits in gasoline direct injection engines and / or port fuel injection engines by preventing or removing deposits. In some embodiments, the composition is used in fuel to reduce deposits in GDI engines. In other embodiments, the disclosed compositions are used to reduce deposits in both GDI engines and PFI engines.

[0014] The fuel composition may contain gasoline, oxygenated compounds, or mixtures thereof as fuel. Based on the total weight of the fuel composition, the disclosed composition may be present in the fuel composition at a concentration of 25 ppm to 1000 ppm. A method for reducing carbon deposits in gasoline engines is also disclosed. Attached Figure Description

[0015] Figure 1 It is a graph showing the fouling of injectors without added fuel.

[0016] Figure 2 This is a graph showing the effectiveness of HDSA / DMAPA detergent in removing jetting deposits.

[0017] Figure 3 This is a graph showing the effectiveness of OHA / DMAPA detergent in removing jet deposits.

[0018] Figure 4 It shows 550M n A graph showing the effectiveness of PIBSA / APDEA detergent in removing jetting deposits.

[0019] Figure 5 It shows 550M n A graph showing the effectiveness of PIBSA / DMAPA detergent in removing jetting deposits.

[0020] Figure 6 This shows 550M quaternized with propylene oxide. nA graph showing the effectiveness of PIBSA / DMAPA detergent in removing jetting deposits.

[0021] Figure 7 This indicates that when used in combination with Mannich detergents and polyetheramines, 550M quaternized with propylene oxide... n A graph showing the effectiveness of PIBSA / DMAP detergent in removing jetting deposits (“Additive Pack 1”).

[0022] Figure 8 This is a graph showing the effect of additive package 2.

[0023] Figure 9 This is a graph showing the effect of additive package 3.

[0024] Figure 10 This is a graph showing the effect of additive pack 4.

[0025] Figure 11 This is a graph showing the effect of the comparison package.

[0026] Figure 12 This is a graph showing the effect of additive package 5.

[0027] Figure 13 This is a graph showing the effect of additive package 6. Detailed Implementation

[0028] The preferred features and implementation schemes will now be described in a non-restrictive manner.

[0029] The additive compositions disclosed herein may comprise acylated detergents, Mannich detergents, and polyethers and / or polyetheramines.

[0030] Acylated detergents can be reaction products of hydrocarbon-substituted acylated agents and nitrogen-containing compounds having at least one optionally quaternized amino group and at least one oxygen or nitrogen atom capable of reacting with the hydrocarbon-substituted acylated agent.

[0031] As used herein, the terms "hydrocarbon substituent" or "hydrocarbon group" are used in their common sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly bonded to the rest of the molecule and exhibiting predominantly hydrocarbon characteristics. Examples of hydrocarbon groups include:

[0032] Hydrocarbon substituents, namely aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic and alicyclic substituted aromatic substituents, as well as cyclic substituents, wherein the ring is completed by another part of the molecule (e.g., two substituents together form a ring).

[0033] Substituted hydrocarbon substituents, i.e. substituents containing non-hydrocarbon groups, in the context of this invention, do not alter the primary hydrocarbon properties of the substituent (e.g., halogens (especially chlorine and fluorine), hydroxyl groups, alkoxy groups, mercapto groups, alkyl mercapto groups, nitro groups, nitroso groups, and thiooxy groups).

[0034] Heterosubstituents, in the context of this invention, are substituents that, while possessing the characteristics of a predominantly hydrocarbon group, contain atoms other than carbon in a ring or chain composed of carbon atoms, and include substituents such as pyridyl, furanyl, thiophene, and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. Typically, for every ten carbon atoms in a hydrocarbon group, there will be no more than two or no more than one non-hydrocarbon substituent; alternatively, non-hydrocarbon substituents may be absent from the hydrocarbon group.

[0035] Hydrocarbon-substituted acylating agents

[0036] The acylating agent with a hydrocarbon substituted group can be a reaction product of a long-chain hydrocarbon, typically a polyolefin substituted with a monounsaturated carboxylic acid reactant, such as (i) α,β monounsaturated C4 to C5. 10 Dicarboxylic acids, such as fumaric acid, itaconic acid, maleic acid; (ii) derivatives of (i), such as anhydrides of (i) or monoesters or diesters derived from C1 to C5 alcohols; (iii) α,β-monounsaturated C3 to C5 alcohols. 10 Monocarboxylic acids, such as acrylic acid and methacrylic acid; or derivatives of (iv)(iii), such as C1 to C5 alcohol-derived esters of (iii), wherein any compound contains an olefin bond represented by the following general formula:

[0037] (R 1 (R) 2 C = C(R) 6 )(CH(R 7 (R) 8 ))(I)

[0038] Where R 1 and R 2 Each of these is independently either hydrogen or a hydrocarbon-based group. R 6 R 7 and R 8 Each of them is independently a hydrogen or hydrocarbon-based group; preferably at least one is a hydrocarbon-based group containing at least 20 carbon atoms.

[0039] Olefin polymers used for reaction with monounsaturated carboxylic acids may include C2 to C4 polymers comprising the majority molar amounts of C2 to C4 polymers. 20Polymers of monoolefins (e.g., C2 to C5 monoolefins). Such olefins include ethylene, propylene, butene, isobutylene, pentene, octene-1, or styrene. The polymer can be a homopolymer such as polyisobutylene, and copolymers of two or more such olefins, such as copolymers of ethylene and propylene; butene and isobutylene; propylene and isobutylene. Other copolymers include a small molar amount of copolymer monomers, for example, 1 mol% to 10 mol% of copolymer monomers being C4 to C5. 18 Those copolymers of dienes, such as copolymers of isobutylene and butadiene; or copolymers of ethylene, propylene and 1,4-hexadiene.

[0040] In another embodiment, the olefinic bonds of formula (I) are primarily vinyl groups, represented by the following formula:

[0041]

[0042] Where R is a hydrocarbon group

[0043]

[0044] Where R is a hydrocarbon group.

[0045] In one embodiment, the vinylidene content of formula (I) may include at least about 30 mol% vinylidene groups, at least about 50 mol% vinylidene groups, or at least about 70 mol% vinylidene groups.

[0046] Therefore, in some embodiments, at least one hydrocarbon substituent of the acylating agent may be C 16 To C 100 hydrocarbon group or C 18 To C 50 Hydrocarbon groups, such as, but not limited to, octadecene groups and / or polyisobutylene groups.

[0047] In some embodiments, the alkyl-substituted acylated agent may be an alkyl-substituted succinic acid and / or an alkyl-substituted succinic anhydride, optionally having a vinylidene content of at least 70 mol%. The alkyl group of the alkyl-substituted succinic acid or anhydride typically contains an average of at least about 8, or about 30, or about 35 to a maximum of about 350, or about 200, or about 100 carbon atoms. In one embodiment, the alkyl group is derived from a polyolefin.

[0048] Therefore, the hydrocarbon substituents are typically derived from polyolefins with a number average molecular weight of 200 to 2000, and in other cases 250 to 1400. In one embodiment, the hydrocarbon group is derived from a number average molecular weight (M... nThe polyolefin is about 200 to at least about 1300, or about 1500, or about 1600 to at most about 5000, or about 3000, or about 2500, or about 2000, or about 1800, and M is a polyolefin. w / M n The molecular weight is approximately 1.0 to approximately 2.0. In some embodiments, the polyolefin has a number-average molecular weight (M). n The polyisobutylene is between 200 and 1000 or 550.

[0049] As used in this article, number-average molecular weight (M n The determination was performed using gel permeation chromatography (“GPC”) (Waters GPC 2000) based on polystyrene standards. The instrument is equipped with a refractive index detector and Waters Empower... TM Data acquisition and analysis software. The column was made of polystyrene (PLgel, 5 μm, purchased from Agilent / Polymer Laboratories, Inc.). For the mobile phase, individual samples were dissolved in tetrahydrofuran and filtered through a PTFE filter before being injected into the GPC port.

[0050] Waters GPC 2000 Operating Conditions :

[0051] Injector, column, and pump / solvent chamber temperature: 40°C

[0052] Autosampler control: Run time: 40 minutes

[0053] Injection volume: 300 μL

[0054] Pump: System pressure: Approximately 90 bar

[0055] (Maximum pressure limit: 270 bar, minimum pressure limit: 0 psi)

[0056] Flow rate: 1.0 ml / min

[0057] Differential refractometer (RI): Sensitivity: -16; Scale factor: 6

[0058] Polyolefins include homopolymers and interpolymers of polymerizable olefin monomers having 2 to about 16, about 6, or about 4 carbon atoms. The olefin can be a monoolefin, such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or a polyolefin monomer, such as a diene monomer, such as 1,3-butadiene and isoprene. In one embodiment, the interpolymer is a homopolymer. An example of the polymer is polybutene. In one case, about 50% of the polybutene is derived from isobutene. Polyolefins are prepared by conventional procedures.

[0059] Nitrogen compounds

[0060] Nitrogen-containing compounds suitable for preparing acylated detergents have at least one amino group and at least one oxygen or nitrogen atom capable of reacting with an acylated agent that can be substituted with a hydrocarbon group. The amino group may optionally be quaternized. Therefore, in some embodiments, the nitrogen-containing compound may have quaternizable oxygen and nitrogen atoms. In other embodiments, the nitrogen-containing compound may have at least two nitrogen atoms, one of which may be a tertiary nitrogen atom, i.e., the nitrogen is quaternizable.

[0061] In one embodiment, a nitrogen-containing compound having an oxygen atom or a nitrogen atom capable of reacting with an acylating agent and also having a tertiary amino group can be represented by the following formula:

[0062]

[0063] Where X is an alkylene group containing about 1 to about 4 carbon atoms; R 2 It is a hydrogen or hydrocarbon group; and R 3 and R 4 It is a hydrocarbon group.

[0064]

[0065] Where X is an alkylene group containing about 1 to about 4 carbon atoms; R 3 and R 4 It is a hydrocarbon group.

[0066] Examples of nitrogen- or oxygen-containing compounds also having a tertiary amine group include, but are not limited to: dimethylaminopropylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylaminoethylamine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, isomers of butylenediamine, pentanediamine, hexanediamine, heptaethylenediamine, diethylenetriamine, dipropylenetriamine, dibutyltriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine or mixtures thereof.

[0067] Nitrogen- or oxygen-containing compounds having a tertiary amino group may also include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazolium and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3'3-aminobis(N,N-dimethylpropylamine). Another type of nitrogen- or oxygen-containing compounds having a tertiary amino group includes alkanolamines, including but not limited to triethanolamine, triethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tri(hydroxyethyl)amine, and N,N,N-tri(hydroxymethyl)amine.

[0068] Acylated detergents

[0069] Hydrocarbon-substituted acylinters and nitrogen-containing compounds can be mixed under conditions suitable for their reaction to form acylated detergents. In some embodiments, when the hydrocarbon-substituted acylinter can be a hydrocarbon-substituted succinic acid and / or a hydrocarbon-substituted succinic anhydride, the reaction conditions can be controlled to produce an imide or amide detergent. If the nitrogen-containing compound contains an oxygen atom, an ester detergent can be formed.

[0070] Methods for preparing imide, amide, or ester detergents using the reaction products disclosed herein are well known in the art. In some embodiments, the acylated detergent can be prepared using a nitrogen-containing compound having a tertiary amino group. However, it should be noted that even when the nitrogen-containing compound used to form the acylated detergent has a tertiary amino group, the acylated detergent does not necessarily need to be quaternized for the purposes disclosed herein.

[0071] Based on the total weight of the composition, the acylated detergent may be present in the composition at 5% to 50% by weight or 10% to 45% by weight.

[0072] Mannich Detergent

[0073] Mannich detergents can be reaction products of hydrocarbon-substituted phenols, aldehydes, and optionally quaternized ammonia or amines. The hydrocarbon substituents are typically derived from polyolefins with a number average molecular weight of 200 to 2000, and in other cases 250 to 1400. There are no excessive limitations on the polyolefins suitable for preparing Mannich detergents and they include polyolefins used in the aforementioned acylated detergents. Therefore, in some embodiments, the hydrocarbon-substituted phenol used to prepare the Mannich detergent can be C 16 To C 100 hydrocarbon group or C 18 To C 50 Hydrocarbon group substitution, such as, but not limited to, octadecene and / or polyisobutylene groups. In some embodiments, the hydrocarbon-substituted phenol may be polyisobutylene, which may optionally have a vinylidene content of at least 60 mol%. In some embodiments, both the acylated detergent and / or the Mannich detergent are composed of hydrocarbon-substituted acylated agents and / or have C 16 To C 100 Or C 18 To C 50 Preparation of phenols with hydrocarbon groups, such as, but not limited to, octadecene groups and / or polyisobutylene groups. In other embodiments, acylated detergents and / or Mannich detergents use the same hydrocarbon-substituted succinic acid and / or hydrocarbon-substituted succinic anhydride (e.g., 550M). n It is prepared by polyisobutylene-substituted succinic acid.

[0074] The aldehyde used to form Mannich detergent can be an aliphatic or aromatic aldehyde. The aldehyde can have 1 to 10 carbon atoms. Aldehydes may include, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, benzaldehyde, and decanal. In one embodiment, the aldehyde is formaldehyde or its reactive equivalent, including trimethylolpropionate formaldehyde. Alkane, paraformaldehyde, and formalin.

[0075] The amines used to form Mannich detergents can be monoamines or polyamines. In either case, they will be formed by formula R. 4 R 5 NH characterization, where R 4 and R 5 Each group is independently hydrogen, hydrocarbon, amino-substituted hydrocarbon, hydroxyl-substituted hydrocarbon, alkoxy-substituted hydrocarbon, or imino group. In some embodiments, R 4 and R 5 Not one of the groups is hydrogen. In this case, they are characterized by the presence of at least one HN< group in their structure, and will have at least one primary amino group (i.e., H2N-) or secondary amino group (i.e., HN<). Examples of monoamines include ethylamine, dimethylamine, diethylamine, n-butylamine, dibutylamine, allylamine, isobutylamine, cocoylamine, stearylamine, laurylamine, methyl laurylamine, oleylamine, N-methyloctylamine, dodecylamine, diethanolamine, morpholine, and octadecylamine. Polyamines have two or more amino groups. The amino groups of polyamines can be primary amino and / or secondary amino and / or tertiary amino, provided that at least one of the amino groups is a primary amino or secondary amino. Polyamines can have two or more carbon atoms. Polyamines can be straight-chain and / or branched and / or cyclic, aliphatic and / or aromatic, and saturated and / or unsaturated. Polyamines can be alkanolamines containing one or more hydroxyl groups. Polyamines may include, for example, alkylene diamines, such as ethylenediamine and propylenediamine, N,N-dimethylethylenediamine, N,N'-diethylpropylenediamine, N,N-dimethylaminopropylamine, and N,N,N'-trimethylethylenediamine; polyethylenepolyamines, such as diethylenetriamine and polyethylenepolyamine substrates, 4-(3-aminopropyl)morpholine, and 2-(2-aminoethylamino)ethanol. In one embodiment of the invention, the amine is an alkylene diamine, including, for example, ethylenediamine and 2-(2-aminoethylamino)ethanol.

[0076] In another embodiment, the amine is a secondary monoamine, an alkylene diamine, or a mixture thereof. In other embodiments, the Mannich detergent can be a reaction product of a polyolefin, formaldehyde, and an amine, wherein the amine is a secondary monoamine, an alkylene diamine, or a mixture thereof, which may optionally be quaternized. Based on the total weight of the composition, the Mannich detergent (unquaternized or quaternized) may be present in the composition at 20% to 80% by weight, or 30% to 70% by weight.

[0077] Quaternized detergents

[0078] In some embodiments, the acylated detergent and / or Mannich detergent may be quaternized. Suitable quaternizing agents may include, but are not limited to, dialkyl sulfates, alkyl halides, hydrocarbon-substituted carbonates, carboxylic acid esters, alkyl esters, hydrocarbon epoxides, combinations of hydrocarbon epoxides and acids, or mixtures thereof. The corresponding amount of quaternized detergent may be the same as that of the unquaternized detergent described above. In some embodiments, the composition comprises a quaternized acylated detergent and an unquaternized Mannich detergent.

[0079] Suitable polyethers and / or polyetheramines ("fluidizing agents")

[0080] The disclosed compositions comprise fluidizing agents, such as polyethers and / or polyether amines. These fluidizing agents may also have detergent properties. Polyether amines can be produced by the formula R[OCH2CH(R...] 1 )]nA represents, where R is a hydrocarbon group, R 1 The group is selected from hydrogen, hydrocarbon groups with 1 to 16 carbon atoms, and mixtures thereof, where n is a number from 2 to about 50, and A is selected from –OCH2CH2CH2NR. 2 R 2 and –NR 3 R 3 , where each R 2 Independently hydrogen or hydrocarbon groups, and each R 3 Independently hydrogen, hydrocarbon group or –[R 4 N(R 5 )]pR 6 , where R 4 For C2-C 10 Alkylene, R 5 and R 6 The alkyl group is independently hydrogen or hydrocarbon, and p is a number from 1 to 7. These polyether amines can be prepared by first condensing an alcohol or alkylphenol with an alkylene oxide, a mixture of alkylene oxides, or several alkylene oxides in a sequential manner at a molar ratio of 1:2 to 50 of hydrogen-containing compounds to alkylene oxides to form a polyether intermediate. U.S. Patent 5,094,667 provides reaction conditions for the preparation of polyether intermediates, the disclosure of which is incorporated herein by reference. In one embodiment, the alcohol can be straight-chain or branched, having 1 to 30 carbon atoms, in another embodiment having 6 to 20 carbon atoms, and in yet another embodiment having 10 to 16 carbon atoms. The alkyl group of the alkylphenol can be 1 to 30 carbon atoms, in another embodiment having 10 to 20 carbon atoms. Examples of alkylene oxides include ethylene oxide, propylene oxide, or butane oxide. The number of alkylene oxide units in the polyether intermediate can be 10 to 35 or 18 to 27. Polyether intermediates can be converted into polyether amines by amination with ammonia, amines, or polyamines to form a polyether amine in which A is -NR.3 R 3 Types of polyetheramines. Published patent application EP310875 provides reaction conditions for the amination reaction, the disclosure of which is incorporated herein by reference. Alternatively, the polyether intermediate can also be converted to a product wherein A is -OCH2CH2CH2NR by reacting with acrylonitrile followed by hydrogenation. 2 R 2 Polyetheramines of this type. U.S. Patent 5,094,667 provides reaction conditions for cyanoethylation and subsequent hydrogenation, the disclosure of which is incorporated herein by reference.

[0081] In another embodiment, the fluidizing agent may be a polyether, which may be derived from formula R 7 O[CH2CH(R 8 )O]qH represents, where R 7 R is a hydrocarbon group. 8 The group is selected from hydrogen, hydrocarbon groups with 1 to 16 carbon atoms, and mixtures thereof, and q is a number from 2 to about 50. The reaction conditions for preparing the polyether and various embodiments of the polyether are presented above in the description of polyether amines as polyether intermediates. A commercial example of the polyether is Lyondell ND. TM Other suitable polyethers are also available from Dow Chemicals, Huntsman, and Akzo.

[0082] In yet another embodiment, the fluidizing agent may be a hydrocarbon-terminated poly(oxyethylene)aminocarbamate, as described in U.S. Patent 5,503,644.

[0083] In another embodiment, the fluidizing agent may be an alkoxylate, wherein the alkoxylate may comprise: (i) a polyether containing two or more ester-terminal groups; (ii) a polyether containing one or more ester groups and one or more terminal ether groups; or (iii) a polyether containing one or more ester groups and one or more terminal amino groups, wherein the terminal group is defined as a group located within five connecting carbon or oxygen atoms from the end of the polymer. Connection is defined as the sum of connecting carbon and oxygen atoms in the polymer or the terminal group.

[0084] Alkoxylates can be represented by formula (VI):

[0085]

[0086] Among them, R 21 It is TC(O)-, where T is a hydrocarbon group derived from butter fatty acids; R 20 It is OH, A, WC(O)-, or a mixture thereof, wherein A is –OCH2CH2CH2NR. 23 R 23 Or –NR24 R 24 , where each R 23 Independently hydrogen or hydrocarbon groups, and each R 24 Independently hydrogen, hydrocarbon group or -[R 25 N(R 26 )]pR 26 , where R 25 C 2-10 -alkylene, each R 26 Independently hydrogen or hydrocarbon group, and p is a number from 1 to 7, W is C 1-36 hydrocarbon group; R 22 X is H, -CH3, -CH2CH3 or a mixture thereof; and X is an integer from 1 to 36.

[0087] Examples of alkoxylates may include: C 12-15 Alcohol-initiated poly(22-24) etheramine, Covestro AGACTACLEAR ND21-A TM (C 12-15 Alcohol-initiated polypropylene oxide (22-24) ether-alcohol, tallow fatty acid-initiated polypropylene oxide (22-24) ester-alcohol, butanol-initiated polypropylene oxide (23-25) ether-tartrate fatty acid ester, dioleoyl glycerol-initiated polypropylene oxide (23-25) ether-alcohol, propylene glycol-initiated polypropylene oxide (33-34) ether-tartrate fatty acid ester, tallow fatty acid-initiated polypropylene oxide (22-24) ester-alcohol, and C 12-15 Alcohol-initiated poly(22-24) ether tallow fatty acid esters.

[0088] These alkoxylated compounds can be prepared by reacting fatty acids such as tall oil fatty acids (TOFA) (i.e., a mixture of fatty acids mainly composed of oleic acid and linoleic acid with residual rosin acid or tallowic acid, i.e., the fatty acid mixture mainly composed of stearic acid, palmitic acid, and oleic acid) with alcohol-terminated polyethers such as polypropylene glycol in the presence of an acidic catalyst (usually methanesulfonic acid). These alkoxylated compounds can also be prepared by reacting dioleoglycerides and propylene oxide in the presence of a catalyst.

[0089] There are no excessive limitations on suitable polyethers and / or polyether amines, and they can be any polyether. In some embodiments, the polyether may have a C0 structure with about 24 propylene oxide units. 12 To C 15 Hydrocarbon groups. Similarly, polyetheramines can have a C group with approximately 24 propylene oxide units. 12 To C 15 Hydrocarbon groups, but nitrogen-capped. In one embodiment, the disclosed composition is of the formula R[OCH2CH(R 1 )]nA represents a polyetheramine, where R is a hydrocarbon group, R1 The group is selected from hydrogen, hydrocarbon groups with 1 to 16 carbon atoms, and mixtures thereof, where n is a number from 2 to about 50, and A is -NR. 3 R 3 , where each R 3 Independently hydrogen, hydrocarbon group or –[R 4 N(R 5 )]pR 6 , where R 4 For C2-C 10 Alkylene, R 5 and R 6 It is independently hydrogen or hydrocarbon-based, and p is a number from 1 to 7. In some embodiments, the fluidizing agent may be a polyether and / or a polyetheramine having detergent properties. Based on the total weight of the composition, the polyether and / or polyetheramine may be present in the composition at 10% to 60% by weight, or 20% to 50% by weight.

[0090] Any of the above compositions can be used in a fuel composition to reduce the formation of carbonaceous deposits in a gasoline engine (such as a gasoline port fuel injection engine or a gasoline direct injection engine). The fuel may contain gasoline, oxygenated compounds, or mixtures thereof. Based on the total weight of the fuel composition, the disclosed compositions may be present in the fuel composition at a concentration of 25 ppm to 2500 ppm or 25 ppm to 1000 ppm, on a base of the active substance.

[0091] organic solvents

[0092] In one embodiment, the fuel composition further comprises (c) an organic solvent. The organic solvent may be added to the detergents disclosed herein or included in a fuel additive package containing acylated detergents and / or Mannich detergents and other fuel additives. The organic solvent may be supplied for homogeneous and liquid detergent compositions and / or fuel additive packages that facilitate treatment. The organic solvent may also be supplied for homogeneous fuel compositions comprising gasoline and an additive composition.

[0093] In some embodiments, the organic solvent may be an aliphatic hydrocarbon or an aromatic hydrocarbon. These types of organic solvents typically boil in the range of about 65°C to 235°C. Aliphatic hydrocarbons include various naphtha and kerosene boiling point fractions having a predominantly aliphatic component. Aromatic hydrocarbons include benzene, toluene, xylene, and various naphtha and kerosene boiling point fractions having a predominantly aromatic component. Additional organic solvents include mixtures of aromatic hydrocarbons and alcohols with aromatic hydrocarbons or kerosene, having a sufficient aromatic hydrocarbon content to make the additive composition fluid at temperatures from about 0°C to -18°C. Based on the total weight of the amine salt and / or additive package, the aliphatic hydrocarbons or aromatic hydrocarbons may be present from about 0% to 70% by weight, 0% to 50% by weight, 0% to 40% by weight, 0% to 35% by weight, or 0% to 30% by weight.

[0094] In some embodiments, the organic solvent may be an alcohol. The alcohol may be an aliphatic alcohol having about 2 to 16 or 2 to 10 carbon atoms. In one embodiment, the alcohol may be ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, pentanol, isoamyl alcohol, 2-methyl-1-butanol, and 2-ethylhexanol. Based on the total weight of the amine salt and / or additive package, the alcohol may be present in the additive composition from about 0% to 40% by weight, 0% to 30% by weight, or 0% to 20% by weight.

[0095] Solvents or combinations thereof may be selected considering cost and throughput to provide improved properties to the additive package, such as improved stability, lower viscosity, or higher flash point. For gasoline and / or oxygenated fuels, the organic solvent may include at least one of 2-ethylhexanol, naphtha, dimethylbenzene (“xylene”), or mixtures thereof. Naphtha may include heavy aromatic naphtha (“HAN”). Therefore, in one embodiment, the organic solvent may include at least one of 2-ethylhexanol, naphtha, dimethylbenzene, or mixtures thereof.

[0096] fuel

[0097] This fuel composition comprises a fuel that is liquid at room temperature and can be used to fuel an engine. The fuel is typically liquid under ambient conditions, such as room temperature (20°C to 30°C). The fuel can be a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof. Hydrocarbon fuels can be hydrocarbons produced by a gas-to-liquid process, including, for example, hydrocarbons produced by processes such as the Fischer-Tropsch process. Hydrocarbon fuels can be petroleum distillates, including gasoline as defined by ASTM specification D4814. In one embodiment, the fuel is gasoline, and in other embodiments, the fuel is leaded or unleaded gasoline. Non-hydrocarbon fuels can be oxygenated compositions, commonly referred to as oxygenated compounds, including alcohols, ethers, ketones, carboxylic esters, nitroalkanes, or mixtures thereof. Non-hydrocarbon fuels may include, for example, methanol, ethanol, butanol, methyl tert-butyl ether, and methyl ethyl ketone. In several embodiments, the fuel may have an oxygenated compound content of 1 vol%, or 10 vol%, or 50 vol%, or up to 85 vol%, based on volume. In other embodiments, the fuel may have an oxygenated content of essentially 100% by volume (minus any impurities or contaminants, such as water). Mixtures of hydrocarbon and non-hydrocarbon fuels may include, for example, gasoline and methanol and / or ethanol. The ethanol may be fuel-grade ethanol according to ASTM D4806. In various embodiments, the liquid fuel may be an emulsion of water in a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof.

[0098] The fuel may include gasoline, an oxygenated compound, or a mixture thereof. In one embodiment, the fuel may contain 0.1 vol% to 100 vol% of an oxygenated compound based on the total volume of the fuel. In another embodiment, the fuel may contain 0.1 vol% to 100 vol% gasoline based on the total volume of the fuel. In yet another embodiment, the oxygenated compound may be ethanol. In other embodiments, the fuel may contain gasoline and 5 vol% to 30 vol% of an oxygenated compound, which may optionally be ethanol.

[0099] Additional performance additives

[0100] The fuel composition described above may also contain one or more additional performance additives. These additional performance additives may be based on several factors, such as the type of internal combustion engine and the type of fuel used in that engine, the quality of the fuel, and the operating conditions of the engine. Additional performance additives may include antioxidants such as hindered phenols or their derivatives and / or diarylamines or their derivatives, and corrosion inhibitors such as alkenyl succinic acid, including PIB succinic acid. Some corrosion inhibitors neutralize acid compounds in the fuel to reduce corrosion. Other corrosion inhibitors reduce corrosion by forming a protective film on the metal surface. When a corrosion inhibitor is added to the fuel in an amount ranging from 1 ppm to 10 ppm or 2 ppm to 3 ppm by weight of the total fuel composition, the corrosion inhibitor is generally effective in reducing corrosion.

[0101] Other additives may include dyes, antibacterial and biocidal agents, gum inhibitors, markers, and demulsifiers, such as polyalkoxylated alcohols. Other additives may include lubricants (such as fatty carboxylic acids), metal passivators (such as aromatic triazoles or their derivatives), and valve seat recess additives (such as alkali metal sulfosuccinates). Additional additives may include antistatic agents, de-icing agents, and combustion improvers (such as octane or cetane number improvers).

[0102] In some embodiments, the additive composition may also contain friction modifiers or anti-wear agents. Friction modifiers can provide enhanced lubrication properties to fuel to reduce wear in the engine or even improve efficiency. Friction modifiers can help reduce wear at the point of fuel injection in the engine. In GDI engines, friction modifiers can reduce wear at the top of the cylinder where fuel is injected. Some of the friction modifiers may also accumulate in the engine oil and also enhance the wear properties of the oil. Friction modifiers can also provide better fuel economy by reducing friction in the engine. Therefore, in some embodiments, the additive composition may contain 5% to 25% by weight or 5% to 15% by weight of friction modifier. Suitable friction modifiers include, but are not limited to, glyceryl monooleate, ethoxylated tallow amine, tall oil fatty acids, or amine salts of succinate acids or succinimides, such as alkylamines or alkanolamines with hydrocarbon-substituted succinic anhydrides. In one embodiment, the friction modifier is tall oil fatty acid. In yet another embodiment, the friction modifier is an amine salt, which is the product of the reaction of N,N-methyldiethanolamine and / or N1-(3-(dimethylamino)propyl)-N3,N3-dimethylpropane-1,3-diamine with hexadecenylsuccinic anhydride.

[0103] The disclosed compositions may be added to fuel as a portion of an additive concentrate or an additive package. Exemplary additive packages (by weight, based on the active substance and the total weight of the additive package) are shown in Table 1 below.

[0104] Table 1

[0105]

[0106]

[0107] *Those skilled in the art will understand that the amount of each additive used in the additive package will be selected such that the total amount will be equal to 100%, even if the ranges listed in the table may not be equal to 100%.

[0108] Industrial applications

[0109] The aforementioned fuel additive compositions and fuels containing such additive compositions can be used in liquid-fuel engines and / or spark-ignition engines, and may include engines for hybrid vehicles and stationary engines. There are no excessive limitations on the type of engine, and it includes, but is not limited to, V-type, inline, opposed, and rotary engines. The engine can be naturally aspirated, turbocharged, electrically supercharged, mechanically supercharged, or turbocharged. The engine can be a carburetor-type or fuel-injected gasoline engine. Therefore, the engine may have a carburetor or injectors (including piezoelectric injectors).

[0110] In one embodiment, the engine may be a gasoline direct injection (“GDI”) engine (injection or wall-guided, or a combination thereof); a port fuel injection (“PFI”) engine; a homogeneous charge compression ignition (“HCCI”) engine; a stoichiometric or lean combustion engine; a spark controlled compression ignition (“SPCCI”) engine; a variable compression, Miller cycle, or Atkinson cycle engine, or a combination thereof, such as an engine that incorporates both GDI and PFI injectors in the same engine. Suitable GDI / PFI engines include 2-stroke or 4-stroke engines that use gasoline, gasoline / alcohol blends, or any of the fuel compositions described above as fuel. The additive composition may reduce wear on the engine (such as a GDI / PFI engine) and / or improve its fuel economy. In other embodiments, the fuel composition may be prepared using an onboard dosing system for GDI engines, PFI engines, or combinations thereof.

[0111] In its embodiments, any of the aforementioned engines may be equipped with a catalyst or device for treating exhaust emissions (e.g., reducing NOx). In other embodiments, the engine may be a flexible fuel engine capable of operating with more than one fuel type (typically gasoline and ethanol or gasoline and methanol). In other embodiments, any of the aforementioned engine types may be found in a hybrid vehicle that also includes an electric motor.

[0112] A method for reducing carbon deposits in an engine is also disclosed. This method may include operating the engine using a fuel composition comprising the aforementioned detergent from an additive package. Based on the total weight of the fuel composition, the detergent may be present in an amount of at least 10 ppm or 20 ppm to 200 ppm (“Keep Clean”), or at least 100 ppm to 500 ppm (“Remove”). It should generally be understood that the Keep Clean treatment rate is a treatment rate sufficient to keep the engine free of carbon deposits; however, the Remove treatment rate is typically a higher concentration to remove the accumulation of carbon deposits in the engine.

[0113] Unless otherwise stated, the amounts of each chemical component mentioned do not include any solvents or diluents that are commonly found in commercial substances, i.e., based on active chemicals. However, unless otherwise stated, each chemical or composition mentioned herein should be interpreted as a commercial-grade substance that may contain isomers, byproducts, derivatives, and other such substances generally understood to be present in commercial-grade forms.

[0114] It is known that some of the substances described above can interact in the final formulation, such that the composition of the final formulation may differ from those initially added. For example, metal ions (e.g., metal ions in detergents) can migrate to other acidic or anionic sites of other molecules. The resulting products, including those formed when the compositions of the present invention are used in their intended purpose, may not be easily described. However, all such conditioning and reaction products are included within the scope of the present invention. The present invention includes compositions prepared by mixing the above-described components.

[0115] The compositions disclosed herein can be used in fuel compositions to reduce the formation of carbon deposits by preventing or removing carbon deposits in engines (such as gasoline direct injection engines), as can be better understood with reference to the following examples.

[0116] Example

[0117] Various acylated detergents are prepared by mixing hydrocarbon-substituted acylated agents with nitrogen-containing compounds.

[0118] Preparation Example A-550M n PIBSA

[0119] 550Mn polyisobutylene (1125g; 2.05mol) was charged into a 2L high-pressure reactor, followed by maleic anhydride (220g; 2.25mol). The batch was then heated to 70°C with stirring (400rpm). Once at this temperature, the container was pressure-tested with nitrogen at 5 bar for 10 minutes to ensure no leaks. The container was then purged with nitrogen four times to ensure the absence of oxygen. The batch was heated to 225°C and held at this temperature for 9 hours. The batch (a light golden viscous liquid) was then cooled to 70°C and decanted.

[0120] Preparation Example 1 was prepared using hexadecenylsuccinic anhydride (“HDSA”) as an acylating agent and dimethylaminopropylamine (“DMAPA”) as a nitrogen-containing compound to form an HDSA / DMAPA acylated detergent. Hexadecenylsuccinic anhydride (650 g: 2.00 mol) was placed in a 2 L flanged flask. Attached to the flanged flask was a Dean Stark water condenser, thermocouple, nitrogen inlet, and a dropping funnel with an immersion tube. The temperature was set at 60 °C, the stirring at 200 rpm, and the nitrogen atmosphere at 0.5 standard cubic feet per hour (“SCFH”). When the reaction reached 60 °C, DMAPA (204.9 g: 2.00 mol) was added dropwise over 60 minutes via the dropping funnel. The reaction was then heated to 135 °C and maintained at this temperature for 7 hours. The reaction was cooled to ambient temperature and then decanted into a storage container. Approximately 35 g of water was collected using a Dean Stark water separator.

[0121] Example 2 describes the preparation of an acylated detergent from oleic acid (“OHA”) and dimethylaminopropylamine. Oleic acid (700 g: 2.48 mol) was placed in a 2 L flanged flask. Attached to the flanged flask was a Dean Stark water condenser, thermocouple, nitrogen inlet, and a dropping funnel with an immersion tube. The temperature was set to 60 °C, the stirring speed to 500 rpm, and the nitrogen flow rate to 0.5 SCFH. When the reaction reached 60 °C, DMAPA (303.3 g: 2.97 mol) was added dropwise over 20 minutes via the dropping funnel. The reaction was then heated to 140 °C and maintained at this temperature for 21 hours. The temperature was then set to 150 °C, and the nitrogen flow rate to 5 SCFH, and the batch was maintained under these conditions for 3 hours to vaporize excess DMAPA. The reaction was then cooled to ambient temperature and decanted into a storage container. Approximately 40 g of water was collected using a Dean Stark water separator.

[0122] Preparation Example 3 was prepared from 550M nAn acylated detergent was prepared from polyisobutylene succinic anhydride (“PIBSA”) and aminopropyl diethanolamine (“APDEA”) to form a PIBSA / APDEA acylated detergent. Preparation Example A (375.1 g: 0.594 mol) was placed in a 1 L flanged flask. Attached to the flanged flask was a Dean Stark water condenser, thermocouple, nitrogen inlet, and a dropping funnel with an immersion tube. The temperature was set to 110 °C, the stirring speed to 200 rpm, and the nitrogen atmosphere to 0.5 SCFH. When the reaction reached 110 °C, aminopropyl diethanolamine (96.4 g: 0.594 mol) was added dropwise over 30 minutes via the dropping funnel. The reaction was slowly heated to 145 °C over 30 minutes and maintained for 150 minutes. The batch was cooled to 100 °C and SO-44 (157.2 g) was added, followed by stirring for another 60 minutes. The reaction was then cooled to ambient temperature and then decanted into a storage container.

[0123] Preparation Example 4 was prepared from 550M n An acylated detergent was prepared from polyisobutylene succinic anhydride (“PIBSA”) and DMAPA to form a PIBSA / DMAPA acylated detergent. Preparation Example A (900 g: 1.40 mol) was placed in a 2 L flanged flask. Attached to the flanged flask was a Dean Stark water condenser, thermocouple, nitrogen inlet, and a dropping funnel with an immersion tube. The temperature was set to 90 °C, the stirring speed to 200 rpm, and the nitrogen atmosphere to 0.5 SCFH. When the reaction reached 90 °C, dimethylaminopropylamine (143.4 g: 1.40 mol) was added dropwise over 60 minutes via the dropping funnel. The reaction was slowly heated to 155 °C over 60 minutes and maintained for 3 hours, with approximately 25 g of water collected in the Dean Stark. The reaction was then cooled to ambient temperature and decanted into a storage container.

[0124] Preparation Example 5 was a PIBSA / DMAPA acylated detergent, which had been quaternized with propylene oxide to form a PIBSA / DMAPA quaternary ammonium salt. The product from Example 4 (600 g: 0.83 mol) was loaded into a 1 L flanged flask, followed by acetic acid (49.6 g: 0.83 mol) and 2-ethylhexanol (135 g). Attached to the flanged flask were an acetone / dry ice condenser, a thermocouple, a nitrogen inlet, and a syringe pump and needle. The temperature was set to 70 °C, the stirring speed to 200 rpm, and the nitrogen atmosphere to 0.1 SCFH. When the reaction reached 70 °C, propylene oxide (86.2 g: 1.49 mol) was added under the surface via the syringe pump and needle over 120 minutes. After the propylene oxide addition was complete, the reaction was maintained at 70 °C for an additional 4 hours. The reaction was then purged with nitrogen to remove excess propylene oxide, cooled to ambient temperature, and then decanted into a storage container.

[0125] The prepared examples were then added to additive-free fuels. For Examples 1-6, different prepared examples were added to the fuels at 200 ppm (mass basis, m / m) of active chemicals. Example 7 shows the CU performance of an additive package containing Example 6 (75 ppm of quaternized acylated detergent m / m active material) plus Mannich detergent and polyetheramine, with a quaternized acylated detergent to Mannich detergent to polyetheramine ratio of 88.2:70.2:37.8 (ppm m / m). The examples are summarized in Table 2 below.

[0126] Therefore, in some embodiments, the disclosed additive composition may comprise:

[0127] a. Acylated detergents, which are reaction products of the following substances:

[0128] i. hydrocarbon-substituted succinic acid and / or hydrocarbon-substituted succinic anhydride; and

[0129] ii. A nitrogen-containing compound having at least one quaternizable amino group and at least one oxygen or nitrogen atom capable of reacting with an acylating agent that substituted the hydrocarbon group;

[0130] b. Mannich detergents, which are reaction products of polyolefins, formaldehyde, and amines; and

[0131] c. Polyetheramine

[0132] The acylated detergent is quaternized with a quaternizing agent, which includes a hydrocarbon epoxide, a combination of a hydrocarbon epoxide and an acid, or a mixture thereof.

[0133] In some embodiments, the additive composition described above may comprise:

[0134] a. 2% to 60% by weight, or 5% to 50% by weight, or 5% to 45% by weight, or 10% to 45% by weight of quaternized acylated detergents;

[0135] b. 5% to 80% by weight, or 20% to 80% by weight, 20% to 75% by weight, 25% to 70% by weight, or 30% to 70% by weight of Mannich detergent; and

[0136] c. 3% to 60% by weight, 10% to 60% by weight, 10% to 55% by weight, or 15% to 50% by weight, or 20% to 50% by weight of polyetheramine.

[0137] In some embodiments, the additive composition described above may comprise:

[0138] a. 5% to 50% by weight of quaternized acylated detergents;

[0139] b. 20% to 80% by weight of Mannich detergent; and

[0140] c. 10% to 60% by weight of polyetheramine.

[0141] In some embodiments, the additive composition described above may comprise:

[0142] a. 10% to 45% by weight of quaternized acylated detergents;

[0143] b. 30% to 70% by weight of Mannich detergent; and

[0144] c. 20% to 50% by weight of polyetheramine.

[0145] The added fuel was then tested to evaluate the cleanliness performance of the prepared example in a Volkswagen (“VW”) GDI engine F-113_VW DISI 01 (engine size). This VW DISI test (CEC-F-113) used a twin-charged Volkswagen (VW) EA111, 1.4-liter, 125kW, 4-cylinder, inline, gasoline direct injection spark ignition (DISI) engine. For the purpose of maintaining cleanliness / contamination or cleanliness, the main test run consisted of a steady-state cycle of 2000 rpm and 56 Nm, with continuous monitoring of the injection pulse width to maintain a stoichiometric air / fuel ratio. Each test began with 48 hours of running the engine rack using no added fuel (referred to as “Haltermann DISI TF low-sulfur” fuel). During this period, the engine control unit adjusted the injector pulse width to ensure sufficient fuel was delivered to the engine when fouling interfered with fuel flow and injection. A preferred way to observe this data is to plot it as a percentage change (%) of the injection pulse width relative to the test duration (hours). Figure 1 The graph for adding fuel is shown. Once 48 hours have passed using the unadded fuel, known as the contamination (DU) phase, the fuel source is switched to the added fuel to begin the cleanup (CU) phase. It is estimated that the CU fuel blend takes approximately 5 to 7 hours to reach the injector, therefore the actual CU is calculated starting at approximately 53 to 55 hours. Injector CU is measured by the rate and amount of change in the injector pulse width. To achieve 100% CU, the injector pulse width must at least return to its original starting point. The CU testing phase lasts 24 hours. The test results are the percentage change in pulse width from the start to the end of the test. The performance of each preparation example and additive package (Example 7) is summarized in Table 2 below. All treatment rates in Table 2 are based on the active material.

[0146] Table 2

[0147]

[0148] Note 1: When the test ended, the scale continued to increase to 12% of the jet pulse width change at about 61 hours and decreased to about 8% of the jet pulse width change at about 81 hours.

[0149] The treatment rate of Additive Pack 1 is 176 ppm. Based on the active ingredients and the total weight of the additive pack, the additive contains 35.9 wt% Mannich detergent, 42.6 wt% quaternized acylated detergent and 21.5 wt% polyetheramine (“PEA”).

[0150] The treatment rate of Additive Pack 2 is 70 ppm. Based on the active ingredients and the total weight of the additive pack, the additive contains 30.6 wt% Mannich detergent, 35.4 wt% quaternized acylated detergent, and 34.0 wt% PEA.

[0151] The treatment rate of C-additive pack 3 was 179 ppm. Based on the active ingredients and the total weight of the additive pack, the additive contained 67.4 wt% Mannich detergent, 13.9 wt% quaternized acylated detergent and 18.7 wt% PEA.

[0152] The treatment rate of D-additive pack 4 is 184 ppm. Based on the active ingredients and the total weight of the additive pack, the additive contains 41.0 wt% Mannich detergent, 13.5 wt% quaternized acylated detergent and 45.5 wt% PEA.

[0153] As shown in Table 2 and Figures 1-10 As shown, the composition protected by the claims is effective in reducing injector deposits in gasoline engines. The type and treatment rate of the acylated detergent can be selected to achieve the desired CU rate. While all the acylated detergents protected by the claims reduce injector deposits, quaternary ammonium acylated detergents appear to clean the engine at an accelerated rate, as can be seen in… Figures 6 to 10 This is seen in the sharp drop in slope.

[0154] Example Group 2

[0155] For Example Group 2, the second group of additive fuels was evaluated in a VW GDI engine using the scheme described above, except that the additive fuel was switched from non-additive to additive fuel at approximately 41 hours, so the additive fuel reached the injectors at approximately 48 hours. This was to ensure that the testing was consistent with the CEC procedure, which requires a 48-hour pollution (DU) phase. The performance of each additive package tested in Example Group 2 is summarized in Table 3 below. All treatment rates in Table 3 are based on the active substance.

[0156] Table 3

[0157]

[0158] Note 1: No clearing was observed after 65 hours.

[0159] A-Comparison pack contains no acylated detergent. Total treatment rate is 154.6 ppm. Based on the active ingredient and the total weight of the additive pack, the additive contains 78.3 wt% Mannich detergent and 21.7 wt% PEA.

[0160] The treatment rate of Additive Pack 5 was 162.7 ppm. Based on the active ingredients and the total weight of the additive pack, the additive contained 74.3 wt% Mannich detergent, 5.0 wt% quaternized acylated detergent, and 20.7 wt% PEA.

[0161] The treatment rate of Additive Pack 6 was 170.8 ppm. Based on the active ingredients and the total weight of the additive pack, the additive contained 70.8 wt% Mannich detergent, 9.5 wt% quaternized acylated detergent, and 19.7 wt% PEA.

[0162] As shown in Table 3, additive package 5 (with quaternized acylated detergent) Figure 12 ) and additive pack 6 ( Figure 13 Compared to the control group (which does not contain acylated detergent), the control group (which does not contain acylated detergent) Figure 11 It is not effective in reducing injector deposits in gasoline engines. Similarly, the treatment rate of acylated detergents can be selected to achieve the desired CU rate, such as with a treatment rate of only 8 ppm of active material. Figure 12 In comparison, a treatment rate of 16 ppm of active material can be observed. Figure 13 The downward slope increases.

[0163] Each of the foregoing references is incorporated herein by reference, including any prior application claiming priority thereto, whether or not specifically listed above. Reference to any reference is not an admission that it is prior art or constitutes general knowledge to a person skilled in the art in any jurisdiction. Unless expressly stated in the examples or otherwise, all numerical quantities of matter, reaction conditions, molecular weight, number of carbon atoms, etc., specified in this specification should be understood to be modified by the word “about.” It should be understood that the upper and lower limits of the quantities, ranges, and proportions described herein can be combined independently. Similarly, the ranges and quantities of each element of the invention can be used in conjunction with the ranges or quantities of any other element.

[0164] As used herein, the transitional term "comprising," synonymous with "comprising," "containing," or "characterized in," is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. However, in every use of "comprising" herein, it is intended that the term also cover the phrases "consistently composed of" and "composed of" as alternative embodiments, wherein "consisting of" excludes any elements or steps not specified, and "consisting of" allows the inclusion of additional, undescribed elements or steps that do not materially affect the essential and novel characteristics of the composition or method under consideration.

[0165] While certain representative embodiments and details have been shown to illustrate the purpose of this invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention. In this respect, the scope of the invention is defined only by the following claims.

Claims

1. Use of an additive composition in a fuel composition for reducing carbon deposits in a gasoline engine, said fuel composition comprising a fuel, said fuel being gasoline, an oxygenated compound, or a mixture thereof, wherein said additive composition comprises: a. An acylated detergent, wherein the acylated detergent is a reaction product of the following substances: i. a hydrocarbyl-substituted acylating agent, wherein the hydrocarbyl-substituted acylating agent is a hydrocarbyl-substituted succinic acid and / or a hydrocarbyl-substituted succinic anhydride, and wherein at least one hydrocarbyl substituent of the acylating agent is a C 16 to C 100 hydrocarbyl group; and ii. A nitrogen-containing compound having at least one optionally quaternized amino group and at least one oxygen or nitrogen atom capable of reacting with an acylating agent that substituted the hydrocarbon group; The acylated detergent is quaternized with a quaternizing agent, which includes dialkyl sulfates, alkyl halides, hydrocarbon-substituted carbonates, carboxylic acid esters, hydrocarbon epoxides, combinations of hydrocarbon epoxides and acids, or mixtures thereof, and wherein the acylated detergent is present in the additive composition at a weight of 5% to 50% based on the total weight of the additive composition. b. 20% to 80% by weight of a Mannich detergent based on the total weight of the additive composition, wherein the Mannich detergent is a reaction product of a hydrocarbon-substituted phenol, aldehyde, and optionally quaternized ammonia or amine; and c. 10% to 60% by weight of polyether and / or polyether amine based on the total weight of the additive composition.

2. The use according to claim 1, wherein the Mannich detergent is quaternized with a quaternizing agent, said quaternizing agent comprising dialkyl sulfates, alkyl halides, hydrocarbon-substituted carbonates, carboxylic acid esters, hydrocarbon epoxides, combinations of hydrocarbon epoxides and acids, or mixtures thereof.

3. The use according to claim 1, wherein the hydrocarbon-substituted phenol used to prepare the Mannich detergent is a polyolefin-substituted phenol having a number average molecular weight of 200 to 2000.

4. The use according to claim 2, wherein the hydrocarbon-substituted phenol used to prepare the Mannich detergent is a polyolefin-substituted phenol having a number average molecular weight of 200 to 2000.

5. The use according to claim 3 or 4, wherein the polyolefin is polyisobutylene.

6. The use according to any one of claims 1 to 4, wherein at least one hydrocarbyl substituent of the acylating agent is a C 18 to C 50 hydrocarbyl group.

7. The use according to claim 6, wherein at least one hydrocarbon substituent of the acylating agent comprises an octadecene group and / or a polyisobutylene group.

8. The use according to claim 6, wherein the acylated detergent is present in the additive composition at a weight of 10% to 45% by weight, based on the total weight of the additive composition.

9. The use according to claim 7, wherein the acylated detergent is present in the additive composition at a weight of 10% to 45% by weight, based on the total weight of the additive composition.

10. The use according to any one of claims 1 to 4, wherein the Mannich detergent is present in the additive composition at a weight of 30% to 70% by weight, based on the total weight of the additive composition.

11. The use according to any one of claims 1 to 4, wherein the polyether and / or polyetheramine are present in the additive composition at a weight of 20% to 50% by weight, based on the total weight of the additive composition.

12. The use according to any one of claims 1 to 4, wherein the additive composition further comprises a friction modifier.

13. The use according to claim 12, wherein the additive composition comprises 5% to 25% by weight of a friction modifier based on the total weight of the additive composition.

14. The use according to claim 12, wherein the friction modifier is tall oil fatty acid.

15. The use according to any one of claims 1 to 4, wherein the gasoline engine is a gasoline direct injection engine.

16. The use according to any one of claims 1 to 4, wherein the gasoline engine is a gasoline intake port fuel injection engine.

17. The use according to claim 1 or 2, wherein the carboxylic ester is an alkyl ester.

18. A fuel composition comprising a fuel and an additive composition, wherein the fuel is gasoline, an oxygenated compound, or a mixture thereof, and the additive composition comprises: a. An acylated detergent, wherein the acylated detergent is a reaction product of the following substances: i. a hydrocarbyl-substituted acylating agent, which is a hydrocarbyl-substituted succinic acid and / or a hydrocarbyl-substituted succinic anhydride, wherein at least one hydrocarbyl substituent of the acylating agent is a C 16 to C 100 hydrocarbyl group and comprises octadecenyl groups and / or polyisobutenyl groups; and ii. A nitrogen-containing compound having at least one quaternizable amino group and at least one oxygen or nitrogen atom capable of reacting with an acylating agent that substituted the hydrocarbon group; The acylated detergent is quaternized with a quaternizing agent, the quaternizing agent comprising at least one hydrocarbon epoxide or a combination of a hydrocarbon epoxide and an acid, and wherein the acylated detergent is present in the additive composition at a weight of 5% to 50% based on the total weight of the additive composition. b. 20% to 80% by weight of a Mannich detergent based on the total weight of the additive composition, wherein the Mannich detergent is a reaction product of a hydrocarbon-substituted phenol, aldehyde, and optionally quaternized ammonia or amine, wherein the hydrocarbon-substituted phenol used to prepare the Mannich detergent is a polyolefin-substituted phenol having a number average molecular weight of 200 to 2000; and c. 10% to 60% by weight of polyether and / or polyether amine based on the total weight of the additive composition. The additive composition is present in the fuel composition at a concentration of 25 ppm to 2500 ppm based on the total weight of the fuel composition.

19. The fuel composition of claim 18, wherein the additive composition is present in the fuel composition at a concentration of 25 ppm to 1000 ppm based on the total weight of the fuel composition.

20. The fuel composition of claim 18, wherein, based on the total volume of the fuel, the fuel comprises 0.1 vol% to 100 vol% of an oxygenated compound or 0.1 vol% to 100 vol% of gasoline.

21. The fuel composition of claim 18, wherein the fuel comprises 5% to 30% by volume of oxygenated compounds based on the total volume of the fuel.

22. The fuel composition according to claim 20 or 21, wherein the oxygen-containing compound is ethanol.

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