Methods and uses relating to combustion of gasoline fuel compositions in direct injection spark ignition engines

Abstract

A method of agglomerating nanoparticles in an exhaust stream resulting from combustion of a gasoline fuel composition in a direct injection spark ignition engine, the method comprising adding one or more quaternary ammonium compounds to the gasoline fuel composition as an agglomeration additive.

Description

[0001] This invention relates to the use of additives in fuel compositions, and particularly to spark-ignition engines. Specifically, the compositions provided by this invention address the problem of nanoparticle emissions from direct-injection spark-ignition engines.

[0002] After more than a century of development, spark ignition (SI) engines have become highly sophisticated engineering devices. Engine designers have developed high-performance engines that include injection systems that inject fuel directly into the cylinders. These engines are also known as direct injection spark ignition (DISI) engines, direct injection gasoline (DIG) engines, gasoline direct injection (GDI) engines, etc.

[0003] Catalytic converters are typically included in the exhaust systems of direct-injection gasoline engines. These converters often include three-way catalytic converters to reduce the release of hydrocarbons, carbon monoxide, and NO into the atmosphere. x The concentration of particulate matter. However, unlike diesel engines where diesel particulate filters are typically installed in the exhaust system, particulate emissions from direct injection gasoline engines are not routinely monitored.

[0004] Nevertheless, particulate matter emissions from direct injection spark ignition engines remain a serious problem. Growing evidence suggests that emissions of nanoparticles, in particular, pose significant risks to human health and are harmful to the environment. While reducing the overall particulate matter emissions from exhaust systems is desirable, reducing the concentration of nanoparticles in emissions is especially important. Nanoparticles are particularly problematic because they are not only more harmful than larger particles, but they are also more difficult to capture, as they can pass through filters.

[0005] The inventors have surprisingly discovered that adding certain additives to fuel can cause nanoparticles to agglomerate into larger particles, which may be more easily captured by filters.

[0006] According to a first aspect of the present invention, a method is provided for agglomerating nanoparticles in the exhaust stream generated by the combustion of a gasoline fuel composition in a direct injection spark ignition engine; the method includes adding one or more quaternary ammonium compounds to the gasoline fuel composition as agglomerating additives.

[0007] According to a second aspect of the invention, the use of one or more quaternary ammonium compounds as agglomerating additives in a gasoline fuel composition is provided for agglomerating nanoparticles in the exhaust stream generated by combustion of the gasoline fuel composition in a direct injection spark ignition engine.

[0008] Preferred features of the first and second aspects of the invention will now be described. Any feature of any aspect may be combined with any feature of any other aspect as desired.

[0009] This invention relates to a method and use of one or more quaternary ammonium compounds as fuel additives. The term "additive" may refer herein to "additive of the present invention" or "agglomeration additive."

[0010] The agglomerative additive may comprise a single quaternary ammonium compound. In some embodiments, a mixture containing more than one quaternary ammonium compound may be used. Therefore, the present invention may relate to the use of a single quaternary ammonium compound, or a mixture of two or more quaternary ammonium compounds. Unless otherwise stated, references herein to “additive” or the “agglomerative additive” or “the additive” or “the agglomerative additive” include embodiments in which a mixture of two or more quaternary ammonium compounds is used.

[0011] The quaternary ammonium compound, or each quaternary ammonium compound suitably, is the product of the reaction of a nitrogen-containing compound having at least one tertiary amine group with a quaternizing agent.

[0012] Nitrogen-containing compounds having at least one tertiary amine group can be selected from any compound containing a tertiary amine functional group.

[0013] Suitable, nitrogen-containing compounds having at least one tertiary amine group may be selected from: (i) The reaction product of a hydrocarbon-substituted acylated agent and a compound having at least one tertiary amine group and a primary amine, secondary amine or alcohol group; (ii) Mannich reaction products containing tertiary amine groups; (iii) A polyalkylene-substituted amine having at least one tertiary amine group; (iv) Equation R 5 R 6 R 7 N-tertiary amines, where R 5 R 6 and R 7 Each can be independently substituted with an alkyl, alkenyl, aryl, alkylaryl, or aralkyl group; (v) cyclic tertiary amines; and (vi) Polyetheramine compounds.

[0014] Nitrogen-containing compounds having at least one tertiary amine group react with quaternizing agents. Any suitable quaternizing agent can be used.

[0015] In some embodiments, nitrogen-containing compounds having at least one tertiary amine group are (i) reaction products of a hydrocarbon-substituted acylating agent and a compound containing at least one tertiary amine group as well as a primary amine, secondary amine, or alcohol group.

[0016] The reaction product of a hydrocarbon-substituted acylating agent with a compound containing at least one tertiary amine group and a primary amine, secondary amine or alcohol group is intended to refer to an amide, ester or imide formed by the reaction of the acylating agent with a primary amine, secondary amine or alcohol group.

[0017] The alkyl-substituted acylinder is suitably a monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, or its reactive equivalent. Its reactive equivalent is a functional group that reacts in the same manner, such as an acyl chloride; or, in the case of a dicarboxylic acid, an anhydride.

[0018] For the avoidance of doubt, a compound containing at least one tertiary amine group and a primary amine, secondary amine or alcohol group is a compound whose molecular structure contains at least one tertiary amine group and at least one additional group selected from primary amine groups, secondary amine groups or alcohol groups.

[0019] The acylating agent reacts with the primary, secondary, or alcohol groups of the compound containing such groups and at least one tertiary amine group to form an ester, amide, or imide compound. The reaction product also contains at least one tertiary amine group and is therefore capable of reacting with the quaternizing agent.

[0020] As those skilled in the art will understand, the reaction of a hydrocarbon-substituted acylating agent with a compound containing a primary amine can provide an amide, or, in the case of a dicarboxylic acid or anhydride, an imide or amide can be formed depending on the reaction conditions.

[0021] The reaction of a hydrocarbon-substituted acylated agent with a compound containing a secondary amine will provide an amide in the reaction product, while the reaction of a hydrocarbon-substituted acylated agent with a compound containing an alcohol functional group will produce an ester.

[0022] Those skilled in the art will understand that the tertiary amine does not react with alkyl-substituted acylating agents. Rather, it is the alcohol, primary amine, or secondary amine group that reacts with the alkyl-substituted acylating agent, and the tertiary amine is present in the reaction product.

[0023] Suitable hydrocarbon-substituted acylated agents used herein include fatty acids, namely compounds of the formula RCOOH, wherein R is an alkyl or alkenyl group having 6 to 36 carbon atoms, preferably 8 to 30 carbon atoms or 12 to 24 carbon atoms. A preferred fatty acid is oleic acid.

[0024] The alkyl-substituted acylating agent may be based on an alkyl-substituted mono-, di-, or polycarboxylic acid or its reactive equivalent. In some preferred embodiments, the alkyl-substituted acylating agent is an alkyl-substituted succinic acid compound, such as an alkyl-substituted succinic acid or succinic anhydride.

[0025] The hydrocarbon substituent preferably contains at least 10, more preferably at least 12, for example 30 or 50 carbon atoms. It may contain up to about 200 carbon atoms. Preferably, the hydrocarbon substituent has a number average molecular weight (Mn) of 170 to 2800, for example 250 to 1500, more preferably 450 to 1500, and even more preferably 450 to 1100. Particularly preferred is an Mn of 700 to 1300.

[0026] The hydrocarbon substituent can be obtained from homopolymers or interpolymers (e.g., copolymers, terpolymers) of mono- and dienes having 2 to 10 carbon atoms (e.g., ethylene, propylene, but-1-ene, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc.). Preferably, these olefins are 1-mono-olefins. The hydrocarbon substituent can also be derived from halogenated (e.g., chlorinated or brominated) analogs of such homopolymers or interpolymers. The hydrocarbon substituent can also be obtained from other sources, such as monomeric high molecular weight olefins (e.g., 1-tetradecene) and their chlorinated and hydrochlorinated analogs, aliphatic petroleum fractions such as paraffin and their cracked and chlorinated analogs and hydrochlorinated analogs, white oils, synthetic olefins such as those produced by the Ziegler-Natta process (e.g., poly(ethylene) fats), and other sources known to those skilled in the art. If desired, any unsaturation in the substituent can be reduced or eliminated by hydrogenation according to procedures known in the art.

[0027] In some preferred embodiments, component (i) comprises the reaction product of a succinic acid derivative with a hydrocarbon-substituted group and an alcohol or amine that also contains a tertiary amine group.

[0028] As used herein, the term "hydrocarbon substituent" or "hydrocarbon group" is used in its common sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and possessing predominantly hydrocarbon properties. Examples of hydrocarbon groups include: (i) Hydrocarbon groups, namely aliphatic (which may be saturated or unsaturated, straight or branched, such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic- and alicyclic-substituted aromatic substituents, and cyclic substituents, wherein the ring is completed by another part of the molecule (e.g., two substituents together form a ring). (ii) Substituted hydrocarbon groups, i.e., substituents containing non-hydrocarbon groups, which, in the context of this invention, do not alter the primary hydrocarbon properties of the substituent (e.g., halogen (such as chlorine, fluorine, or bromine), hydroxyl, alkoxy (e.g., C1 to C4 alkoxy), ketone, acyl, cyano, mercapto, amino, amide, nitro, nitroso, sulfoxide, nitryl, and carboxyl). (iii) Heterosubstituents, which are substituents that, in the context of this invention, have predominantly hydrocarbon properties while containing heteroatoms other than carbon in a ring or chain originally composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and substituents such as pyridyl, furanyl, thiophene, and imidazolyl. Typically, no more than two, preferably no more than one, non-hydrocarbon substituents per ten carbon atoms will be present in the hydrocarbon group; typically, no non-hydrocarbon substituents will be present in the hydrocarbon group.

[0029] In this specification, unless otherwise stated, references to optionally substituted alkyl groups may include aryl-substituted alkyl groups, and references to optionally substituted aryl groups may include alkyl-substituted or alkenyl-substituted aryl groups.

[0030] Preferred hydrocarbon substituents are poly(isobutylene). Such compounds are known in the art. Therefore, in some particularly preferred embodiments, the hydrocarbon-substituted acylated agent is polyisobutylene-substituted succinic acid or succinic anhydride.

[0031] Polyisobutylene-substituted succinic anhydride is particularly preferred.

[0032] The preparation of polyisobutylene-substituted succinic anhydride (PIBSA) is documented in the prior art. Suitable processes include the thermal reaction of polyisobutylene with maleic anhydride (see, for example, US-A-3,361,673 and US-A-3,018,250), or the reaction of halogenated, particularly chlorinated, polyisobutylene (PIB) with maleic anhydride (see, for example, US-A-3,172,892). Alternatively, polyisobutylene-substituted succinic anhydride can be prepared by mixing a polyolefin with maleic anhydride and passing chlorine gas through the mixture (see, for example, GB-A-949,981).

[0033] Both conventional polyisobutylene and so-called “highly reactive” polyisobutylene are applicable to this invention. In this context, highly reactive polyisobutylene is defined as having at least 50%, preferably 70% or more of terminal olefinic double bonds of the vinylidene type as described in EP0565285. Particularly preferred polyisobutylenes are those having more than 80 mol% and at most 100% terminal vinylides as described in EP1344785.

[0034] Those skilled in the art will understand that in the preparation of PIBSA from the reaction of PIB with maleic acid (MA), a mixture of products is obtained. Typically, the reaction mixture comprises some unreacted PIB, some PIBSA from the reaction of PIB with one MA (monomaleicated PIBSA), and some PIBSA from the reaction of PIB with two MAs (bismaleicated PIBSA). The fraction of bismaleicated product as a percentage of the total PIBSA product can be referred to as the bismaleication level (BML). Suitable PIBSA for the preparation of additive (i) may have a BML of up to 90%, suitably up to 70%, for example 1 to 50% or 2 to 30%.

[0035] Other preferred hydrocarbon groups include those having an internal olefin, such as those described by the applicant in published application WO2007 / 015080.

[0036] As used herein, internal olefins refer to any olefin that primarily comprises non-α double bonds, i.e., β or higher olefins. Preferably, such materials are substantially entirely β or higher olefins, for example containing less than 10% by weight of α olefins, more preferably less than 5% by weight or less than 2% by weight. Typical internal olefins include Neodene 1518 IO, which is available from Shell.

[0037] Internal alkenes are sometimes also called isomerized alkenes and can be prepared from α-olefins by isomerization processes known in the art, or obtained from other sources. The fact that they are also called internal alkenes reflects that they do not necessarily have to be prepared by isomerization.

[0038] In some preferred embodiments, the additives of the present invention comprise the quaternization reaction product of an alcohol or amine (including a tertiary amine) with an optionally substituted succinic acid of formula (A1) or (A2) or its anhydride: Where R 1 The hydrocarbon group is optionally substituted. R is preferred. 1 The substituted alkyl or alkenyl groups are optional.

[0039] R 1 It may be substituted by one or more groups selected from halogen (such as chlorine, fluorine or bromine), nitro, hydroxyl, mercapto, sulfoxide, amino, nitroacyl, acyl, carboxyl, alkyl (e.g. C1 to C4 alkyl), alkoxy (e.g. C1 to C4 alkoxy), amide, ketone, sulfoxide and cyano.

[0040] Preferred R 1 It is an unsubstituted alkyl or alkenyl group. This substituted succinic acid or anhydride can be suitably prepared by reacting maleic anhydride with an olefin.

[0041] In some preferred embodiments, R 1It has a number average molecular weight of 100 to 5000, preferably 300 to 4000, suitably 450 to 2500, for example 450 to 2000 or 450 to 1500.

[0042] In a particularly preferred embodiment, the additive of the present invention comprises a quaternary ammonium compound prepared from the reaction product of a polyisobutylene-substituted hydrocarbon-substituted succinic acid or its anhydride having a number average molecular weight of 450 to 1500 and an alcohol or amine further comprising a tertiary amino group.

[0043] In some embodiments, the substituted succinic acid or its anhydride may contain R with different lengths. 1 A mixture of compounds containing the group R. In such embodiments, reference to the group R is made. 1 The molecular weight refers to the number-average molecular weight of all such groups in all compounds of the composition.

[0044] In the preferred embodiment, R 1 It is polyisobutylene-based, preferably having a number average molecular weight of 100 to 5000, more preferably 200 to 2400, and suitably 450 to 1500.

[0045] In some implementation schemes, R 1 C1 to C are optional replacements 500 Alkyl or alkenyl, for example C8 to C9 40 Alkyl or alkenyl, appropriately C 16 To C 36 Alkyl or alkenyl groups.

[0046] In some embodiments, the additives of the present invention comprise quaternary ammonium compounds, which are composed of C 10 To C 30 C is preferred 20 To C 24 Prepared by reacting alkyl or alkenyl succinic acids or anhydrides with amines or alcohols containing tertiary amino groups.

[0047] The preferred hydrocarbon-substituted acylation agents used herein are polyisobutylene-substituted succinic anhydride or PIBSA. Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300 to 2800, preferably 450 to 2300, more preferably 500 to 1300.

[0048] This alkyl-substituted succinic acid-derived acylating agent is suitably prepared by reacting maleic anhydride with an olefin (e.g., polyisobutylene). The resulting product (such as PIBSA) still contains a double bond. The maleic anhydride exists as the succinic acid moiety in the resulting molecule. The initial product is monomaleicated PIBSA.

[0049] Monomaleic acid-modified PIBSA may have structure (A) or (B): The double bond in the monomaleic acid product can react with another molecule of maleic anhydride to form a dimaleic acid-modified PIBSA with structure (C) or (D): Therefore, it is possible to provide hydrocarbon groups that are substituted by more than one succinic acid moiety.

[0050] Those skilled in the art will understand that the alkyl-substituted succinic acid-derived acylation agents used in this invention typically comprise mixtures of compounds, such as a mixture of mono- and bis-maleic acid-modified PIBSA. The PIBSA can be defined according to its level of bis-maleic acid modification.

[0051] One approach is to determine it by calculating the average number of succinic acid portions per molecule of acylated agent.

[0052] Monomaleic acid-modified PIBSA has one succinic acid portion per module.

[0053] Dimaleated PIBSA has two succinic acid moieties per molecule.

[0054] A mixture containing monomaleic PIBSA and bismaleic PIBSA in a molar ratio of 1:1 will contain an average of 1.5 succinic acid fractions per molecule of PIBSA.

[0055] The average number of succinic acid portions per molecule of acylating agent is sometimes referred to in the industry as the "P-value".

[0056] Suitable, the quaternary ammonium compound, or each quaternary ammonium compound, is prepared by an acylating agent derived from succinic acid and comprising an average of 1 to 2 succinic acid moieties per molecule, with a hydrocarbon group substituted.

[0057] In some preferred embodiments, the invention may relate to the use of quaternary ammonium compounds derived from hydrocarbon-substituted acylating agents comprising an average of at least 1.2 succinic acid moieties per molecule.

[0058] As those skilled in the art will understand, a single molecule cannot have 1.2 succinic acid moieties. At least 1.2 succinic acid moieties means the average number of succinic acid moieties per molecule of acylating agent, which is equal to the sum of all succinic acid moieties present in the sample divided by the total number of acylating agent molecules present in the sample that have one or more succinic acid moieties.

[0059] Preferably, the acylated agent derived from succinic acid by the hydrocarbon group substitution contains an average of at least 1.21 succinic acid moieties per molecule, more preferably at least 1.22 succinic acid moieties per molecule.

[0060] In some embodiments, the hydrocarbon-substituted succinic acid-derived acylated agent may contain at least 1.23 or at least 1.24 succinic acid moieties per molecule.

[0061] In some embodiments, the hydrocarbon-substituted succinic acid-derived acylated agent may contain at least 1.25, at least 1.26, or at least 1.27 succinic acid moieties per molecule.

[0062] In some embodiments, the hydrocarbon-substituted succinic acid-derived acylated agent may contain at least 1.28, at least 1.29, or at least 1.30 succinic acid moieties per molecule.

[0063] The succinic acid moiety refers to succinic acid residues that exist in the form of diacids or anhydrides.

[0064] The hydrocarbon-substituted acylating agent reacts with a compound capable of reacting with the acylating agent and containing a tertiary amine group. The tertiary amine group is quaternized to provide a quaternary ammonium compound.

[0065] Examples of suitable compounds capable of reacting with alkyl-substituted succinic acid-derived acylating agents and containing a tertiary amine group include, but are not limited to: N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, and N,N-dimethylaminoethylamine. Nitrogen- or oxygen-containing compounds capable of condensing with acylating agents and further having a tertiary amine 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). Other types of nitrogen- or oxygen-containing compounds that can condense with acylating agents and have a tertiary amino group include alkanolamines, including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-dimethylaminoethanol, N,N-diethylaminopropanol, N,N-diethylaminoethanol, N,N-diethylaminobutanol, N,N,N-tri(hydroxyethyl)amine, N,N,N-tri(hydroxymethyl)amine, N,N,N-tri(aminoethyl)amine, and N,N-dibutylamine. propylamine and N,N,N'-trimethyl-N'-hydroxyethyl-diaminoethyl ether; N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol, N,N,N'-trimethylaminoethylethanolamine and 3-(2-(dimethylamino)ethoxy)propylamine.

[0066] Type (i) of preferred nitrogen-containing compounds having at least one tertiary amino group is formed by the reaction of a hydrocarbon-substituted acylating agent with an amine of formula (B1) or (B2): Where R 1 C1 to C 36 Alkyl, aryl, alkylaryl, or aralkyl; R 2 and R 3 X is an alkyl group having 1 to 36 carbon atoms, whether identical or different; n is an alkylene group having 1 to 20 carbon atoms; m is 0 to 20; and R is 1 to 5. 4 Hydrogen or C1 to C 36 alkyl.

[0067] In order to form the quaternary ammonium compound used in this invention, the quaternizing agent can be reacted with a compound formed by reacting a hydrocarbon-substituted acylating agent with an amine of formula (B1) or (B2).

[0068] When using compounds of formula (B1), R 4 Preferably hydrogen or C1 to C 16 Alkyl groups, preferably C1 to C2 10 Alkyl, more preferably C1 to C6 alkyl. When R 4 When it is alkyl, it can be linear or branched. It can be substituted, for example, by hydroxyl or alkoxy substituents. R is preferred. 4 Not a substituted alkyl group. More preferably R 4 Selected from hydrogen, methyl, ethyl, propyl, butyl, and their isomers. R is the most preferred. 4 It is hydrogen.

[0069] When using compounds of formula (B2), each R 4 Preferably hydrogen or C1 to C6 alkyl. More preferably, each R 4 Selected from hydrogen, methyl, ethyl, propyl, butyl, and their isomers. The most preferred is each R... 4 It can be hydrogen or methyl.

[0070] When using a compound of formula (B2), m is preferably 2 or 3, most preferably 2; n is preferably 0 to 15, more preferably 0 to 10, and even more preferably 0 to 5. Most preferably n is 0, and the compound of formula (B2) is an alcohol.

[0071] In some preferred embodiments, the hydrocarbon-substituted acylated agent reacts with a diamine compound of formula (B1).

[0072] R 2 and R 3 These can be the same or different alkyl, alkenyl, or aryl groups having 1 to 22 carbon atoms. In some embodiments, R 2 and R 3 They can connect together to form a ring structure, such as a piperidine or imidazole moiety. R 2 and R 3 It can be a branched alkyl or alkenyl group. Each can be substituted, for example, by a hydroxyl or alkoxy substituent.

[0073] R 2 and R 3 Each can be independently defined as C1 to C 16 Alkyl groups, preferably C1 to C2 10 Alkyl group. R 2 and R 3 It can be independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or any isomer thereof. R is preferred. 2 and R 3 Each is independently a C1 to C4 alkyl group. R is preferred. 2 It is methyl. R is preferred. 3 It is a methyl group.

[0074] X is a bond or an alkylene group having 1 to 20 carbon atoms. In a preferred embodiment, when X is an alkylene group, the group can be straight-chain or branched. The alkylene group may contain a cyclic structure. It may be optionally substituted, for example, by a hydroxyl or alkoxy substituent. In some embodiments, the alkylene group may optionally be interrupted by one or more heteroatoms (e.g., O, NH, or N-alkyl).

[0075] X is preferably an alkylene group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example 2 to 6 carbon atoms or 2 to 5 carbon atoms. Most preferably X is ethylene, propylene, or butylene, especially propylene.

[0076] Examples of suitable (B1) compounds used herein include 1-aminopiperidine, 1-(2-aminoethyl)piperidine, 1-(3-aminopropyl)-2-piperacline, 1-methyl-(4-methylamino)piperidine, 4-(1-pyrrolyl)piperidine, 1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1-methylpyrrolidine, N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-dibutylethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-dimethyl-1,3-diaminopropane, N,N,N'-trimethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N,N'-triethylethylenediamine, 3-dimethylaminopropylamine, 3-Diethylaminopropylamine, 3-Dibutylaminopropylamine, N,N,N'-Trimethyl-1,3-propanediamine, N,N,2,2-Tetramethyl-1,3-propanediamine, 2-Amino-5-Diethylaminopentane, N,N,N',N'-Tetraethyldiethylenetriamine, 3,3'-Diamino-N-methyldipropylamine, 3,3'-Iminobis(N,N-Dimethylpropylamine), 1-(3-Aminopropyl)imidazolium and 4-(3-Aminopropyl)morpholine, 1-(2-Aminoethyl)piperidine, 3,3-Diamino-N-methyldipropylamine, 3,3-Aminobis(N,N-Dimethylpropylamine), N'-(3-(Dimethylamino)propyl)-N,N-Dimethyl1,3-propanediamine, 3-(2-(Dimethylamino)ethoxy)propylamine or combinations thereof.

[0077] In some preferred embodiments, the compound of formula (B1) is selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, or combinations thereof.

[0078] The most preferred compound of formula (B1) is dimethylaminopropylamine.

[0079] Examples of suitable (B2) compounds used herein include alkanolamines, including but not limited to triethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamino)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol; triethanolamine, N,N,N-tri(hydroxymethyl)amine, N,N,N-tri(aminoethyl)amine, N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine and N-(3-dimethylaminopropyl)-N,N-diisopropanolamine.

[0080] In some preferred embodiments, the compound of formula (B2) is selected from N,N-dimethylaminopropanol, triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamine)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, or combinations thereof.

[0081] The most preferred compound of formula (B2) is dimethylaminopropanol.

[0082] Some preferred acylating agents used in the preparation of the quaternary ammonium compounds of this invention are polyisobutylene-substituted succinic acid or succinic anhydride. When the compound of formula (B2) reacts with a succinic acid acylating agent, the product obtained is a succinate. When the succinic acid acylating agent reacts with a compound of formula (B1) (wherein R...) 4 When reacted with a succinic acid acylated agent (where R is hydrogen), the product can be succinimide or succinamide. 4 When the hydrogen is not present, the product obtained is an amide.

[0083] Therefore, in some embodiments, component (i) may be the product of a reaction between a succinic acid derivative and an amine or alcohol (which is an ester or amide and also includes an additional unreacted carboxylic acid group). When used in excess, this additional carboxylic acid functional group may react with another amine or alcohol to form a diester or diamide.

[0084] For the avoidance of doubt, succinates include monoester compounds having the general formula (C1) and diester compounds having the general formula (C2); succinimides have the general formula (C3); and succinamides include monoamide compounds having the general formula (C4) and diamide compounds having the general formula (C5). It will be understood that (C1) and (C4) isomers can be formed, in which other carboxylic acid groups are esterified / amidated.

[0085] The group R' shown in Figures (C1) to (C5) contains a tertiary amino group. This group can be quaternized by reacting with a quaternizing agent. For compounds of formula (C2) or (C5) containing two tertiary amino groups, each of these groups can be reacted with a quaternizing agent to provide a diquaternary ammonium compound containing two cationic moieties. This type of compound is used to provide a diquaternary ammonium compound containing two cationic moieties. This type of compound (used as a diesel fuel cleaner) is described in US9365787.

[0086] In some embodiments, a mixture of compounds having formulas (C1) and (C2) or a mixture containing compounds (C3) and / or (C4) and / or (C5) may be used.

[0087] In a preferred embodiment, the succinic acid derivative reacts with an amine (including a tertiary amine group) under conditions that form succinimide.

[0088] In some embodiments, the acid / anhydride reacts with the alcohol / amine in a molar ratio of 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 2:1 to 1:2, for example 1.5:1 to 1:1.5.

[0089] The preferred reaction is between the acid / anhydride and the alcohol / amine at a molar ratio of about 1:1, for example, from 1.2:1 to 1:1.2.

[0090] Suitable, the agglomerating additive of the present invention comprises a quaternary ammonium compound prepared from the reaction product of an optionally substituted succinic acid or its anhydride (preferably a hydrocarbon-substituted succinic acid or its anhydride) and an alcohol or amine selected from dimethylaminopropanol, dimethylaminopropylamine, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine or combinations thereof.

[0091] In some particularly preferred embodiments, the agglomerating additive of the present invention comprises a quaternary ammonium compound prepared from a tertiary amine (i), wherein the tertiary amine is prepared from an amine containing a tertiary amino group (e.g., dimethylaminopropylamine) and a succinic anhydride substituted with polyisobutylene. The number average molecular weight of the polyisobutylene substituent is preferably from 450 to 1300, more preferably from 900 to 1100.

[0092] The agglomerating additives of the present invention, comprising compounds derived from tertiary amines (i), can be prepared by any suitable method. Such methods will be known to those skilled in the art and are exemplified herein. Typically, quaternary ammonium compounds are prepared by heating a quaternizing agent and a compound prepared by reacting a hydrocarbon-substituted acylating agent with an amine of formula (B1) or (B2) in a solvent at a molar ratio of about 1:1. The resulting crude reaction mixture can be added directly to gasoline fuel, optionally after the solvent has been removed. No byproducts or residual starting materials remaining in the mixture have been found to cause any impairment to the performance of the additive. Therefore, the present invention provides a gasoline fuel composition comprising a reaction product of a quaternizing agent with a hydrocarbon-substituted acylating agent and an amine of formula (B1) or (B2).

[0093] In some embodiments, the quaternary ammonium compound used in this invention is a quaternization reaction product of a fatty acid (e.g., oleic acid) and a compound of formula (B1) or (B2) (e.g., dimethylaminopropylamine).

[0094] In some embodiments, the nitrogen-containing class having at least one tertiary amine group can be (ii) a Mannich reaction product containing a tertiary amine. The preparation of quaternary ammonium compounds formed from nitrogen-containing classes containing component (ii) is described in US2008 / 0052985.

[0095] The Mannich reaction products with tertiary amine groups are prepared by reacting hydrocarbon-substituted phenols, aldehydes, and amines.

[0096] The hydrocarbon substituent of this alkyl-substituted phenol may have 6 to 400 carbon atoms, suitably 30 to 180 carbon atoms, for example 10 or 40 to 110 carbon atoms. The hydrocarbon substituent may be derived from an olefin or a polyolefin. Useful olefins include α-olefins, such as commercially available 1-decene.

[0097] Polyolefins that can form hydrocarbon substituents can be prepared by polymerizing olefin monomers using polymerization methods well known in the art, and are also commercially available.

[0098] Some preferred polyolefins include polyisobutylene with a number average molecular weight of 400 to 3000, in another example 400 to 2500, and in a further example 400 or 450 to 1500.

[0099] This hydrocarbon-substituted phenol can be prepared by alkylating the phenol with the aforementioned olefin or polyolefin (e.g., polyisobutylene or polypropylene) using a known alkylation method.

[0100] In some embodiments, the phenol may contain low molecular weight alkyl substituents, such as phenols carrying one or more alkyl chains with a total of less than 28 carbon atoms, preferably less than 24 carbon atoms, more preferably less than 20 carbon atoms, preferably less than 18 carbon atoms, preferably less than 16 carbon atoms, and most preferably less than 14 carbon atoms.

[0101] Monoalkylphenols may be preferred, suitably having 4 to 20 carbon atoms, preferably 6 to 18, more preferably 8 to 16, and especially 10 to 14 carbon atoms, such as phenols having C12 alkyl substituents.

[0102] The aldehydes used to form the products of the Mannich reaction can have 1 to 10 carbon atoms and are usually formaldehyde or its reactive equivalents such as formalin or paraformaldehyde.

[0103] The amine used to form the product of the Mannich reaction can be a monoamine or a polyamine.

[0104] Examples of monoamines include, but are not limited to, ethylamine, dimethylamine, diethylamine, n-butylamine, dibutylamine, allylamine, isobutylamine, cocoamine, stearamine, laurylamine, methyl laurylamine, oleylamine, N-methyloctylamine, dodecylamine, diethanolamine, morpholine, and octadecylamine.

[0105] Suitable polyamines can be selected from any compound containing two or more amine groups. Suitable polyamines include polyalkylene polyamines, for example, wherein the alkylene component has 1 to 6, preferably 1 to 4, and most preferably 2 to 3 carbon atoms. Preferred polyamines are polyethylene polyamines.

[0106] The polyamine has 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, and more preferably 2 to 8 nitrogen atoms.

[0107] In a particularly preferred embodiment, the amine used to form the Mannich reaction product comprises a diamine. Suitably, it includes primary or secondary amines that participate in the Mannich reaction, as well as additional tertiary amines.

[0108] In a preferred embodiment, component (ii) comprises a product obtained directly from the Mannich reaction and containing a tertiary amine. For example, the amine may comprise a single primary or secondary amine that, when reacted in the Mannich reaction, forms a tertiary amine capable of being quaternized. Alternatively, the amine may comprise a primary or secondary amine capable of participating in the Mannich reaction and a tertiary amine capable of being quaternized. However, component (ii) may comprise a compound obtained from the Mannich reaction and subsequently reacted to form a tertiary amine, for example, the Mannich reaction may produce a secondary amine that is subsequently alkylated to a tertiary amine.

[0109] In some embodiments, the nitrogen-containing compound class containing at least one tertiary amine group is (iii) a polyalkylene-substituted amine having at least one tertiary amine group.

[0110] The preparation of nitrogen-containing quaternary ammonium compounds, including component (iii), is described, for example, in US2008 / 0113890.

[0111] The polyolefin-substituted amines of the present invention having at least one tertiary amino group can be derived from olefin polymers and amines (e.g., ammonia, monoamines, polyamines, or mixtures thereof). They can be prepared by a variety of methods, such as those described and mentioned in US2008 / 0113890.

[0112] Suitable preparation methods include, but are not limited to: reacting halogenated olefin polymers with amines; reacting hydroformylated olefins with polyamines and hydrogenating the reaction product; converting polyolefins into the corresponding epoxides and converting the epoxides into polyolefin-substituted amines by reductive amination; and hydrogenation of β-amino nitrile.

[0113] The olefin monomers of the derived olefin polymers include polymerizable olefin monomers characterized by the presence of one or more olefinically unsaturated groups, such as ethylene, propylene, 1-butene, isobutene, 1-octene, 1,3-butadiene, and isoprene.

[0114] Olefin monomers are typically polymerizable terminal olefins. However, polymerizable internal olefin monomers can also be used to form polyolefins.

[0115] Examples of terminal and internal olefin monomers that can be used to prepare polyolefins using conventional, well-known polymerization techniques include: ethylene; propylene; butene, including 1-butene, 2-butene, and isobutene; 1-pentene; 1-hexene; 1-heptene; 1-octene; 1-nonene; 1-decene; 2-pentene; propylene tetramer; diisobutene; isobutene trimer; 1,2-butadiene; 1,3-butadiene; 1,2-pentadiene; 1,3-pentadiene; 1,4-pentadiene; isoprene; 1,5-hexadiene; 2-methyl-5-propyl-1-hexene; 3-pentene; 4-octene; and 3,3-dimethyl-1-pentene.

[0116] Appropriately, the polyolefin substituents of the polyolefin-substituted amines are derived from polyisobutylene.

[0117] Amines that can be used to prepare polyolefin-substituted amines include ammonia, monoamines, polyamines, or mixtures thereof, including mixtures of different monoamines, mixtures of different polyamines, and mixtures of monoamines and polyamines (including diamines). These amines include aliphatic, aromatic, heterocyclic, and carbocyclic amines.

[0118] Monoamines and polyamines suitably contain at least one primary or secondary amine group.

[0119] Suitable monoamines are typically substituted with a hydrocarbon group having 1 to about 50 carbon atoms, preferably 1 to 30 carbon atoms. Saturated aliphatic hydrocarbon groups are particularly preferred.

[0120] Examples of suitable monoamines include methylamine, ethylamine, diethylamine, 2-ethylhexylamine, di-(2-ethylhexyl)amine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoylamine, stearylamine, laurylamine, methyl laurylamine, and oleylamine.

[0121] Aromatic monoamines include those in which the carbon atom of the aromatic ring structure is directly attached to the nitrogen atom of the amine. Examples of aromatic monoamines include aniline, di(p-methylphenyl)amine, naphthylamine, and N-(n-butyl)aniline.

[0122] Examples of aliphatic-substituted, alicyclic-substituted, and heterocyclic-substituted aromatic monoamines include p-dodecylaniline, cyclohexyl-substituted naphthylamine, and thiophene-substituted aniline, respectively.

[0123] Hydroxylamines are also included in the category of useful monoamines. Examples of hydroxylated monoamines include ethanolamine, di-3-propanolamine, 4-hydroxybutylamine, diethanolamine, and N-methyl-2-hydroxypropylamine.

[0124] The amine in a polyolefin-substituted amine can be a polyamine. This polyamine can be aliphatic, alicyclic, heterocyclic, or aromatic.

[0125] Examples of suitable polyamines include alkylene polyamines, hydroxyl polyamines, aryl polyamines, and heterocyclic polyamines.

[0126] Ethylene polyamines are particularly useful due to their cost and efficiency. Suitable ethylene polyamines are described in the first aspect.

[0127] Suitable hydroxyl-containing polyamines include hydroxyalkylalkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atom, and can be prepared by reacting the alkylene polyamine with one or more epoxides. Examples of suitable hydroxyalkyl-substituted polyamines include: N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine, monohydroxypropyl-substituted diethylenetriamine, dihydroxypropyl-substituted tetraethylenepentamine, propyl, and N-(3-hydroxybutyl)tetramethylenediamine.

[0128] Suitable aryl polyamines are similar to the aromatic monoamines described above, except that they contain another amino nitrogen in their structure. Some examples of aryl polyamines include N,N'-di-n-butyl-p-phenylenediamine and bis(p-aminophenyl)methane.

[0129] Suitable heterocyclic monoamines and polyamines will be known to those skilled in the art. Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-diaminoethylpiperazine. Hydroxycyclic polyamines, such as N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine, p-hydroxyaniline, and N-hydroxyethylpiperazine, may also be used.

[0130] Examples of polyolefin-substituted amines may include: poly(propylene)amine, poly(butene)amine, N,N-dimethylpolyisobutyleneamine; N-polybutenemorpholine, N-poly(butene)ethylenediamine, N-poly(propylene)trimethylenediamine, N-poly(butene)diethylenetriamine, N',N'-poly(butene)tetraethylenepentamine and N,N-dimethyl-N'poly(propylene)-1,3propylenediamine.

[0131] The number average molecular weight of polyolefin-substituted amines can be 500 to 5000, or 500 to 3000, for example 1000 to 1500.

[0132] In some embodiments, nitrogen-containing compounds having at least one tertiary amine group are (iv) formula R 5 R 6 R 7 N-tertiary amines, where R 5 R 6 and R 7 Each can be independently substituted with an alkyl, alkenyl, aryl, alkylaryl, or aralkyl group.

[0133] In some embodiments of the present invention, formula R 5 R 6 R 7The tertiary amine of N can be a small compound with low complexity and low molecular weight. In some embodiments, the tertiary amine can be a complex molecule containing a tertiary amine group and / or a high molecular weight molecule.

[0134] Formula R 5 R 6 R 7 Tertiary amine compounds of N preferably do not contain any primary or secondary amine groups. In some embodiments, they may be derived from compounds containing these groups, but preferably these groups have subsequently been reacted to form additional tertiary amine classes. Formula R 5 R 6 R 7 Tertiary amine compounds of N may contain more than one tertiary amine group. However, tertiary amine compounds containing primary or secondary amine groups are within the scope of this invention, provided that these groups do not impede the quaternization of the tertiary amine class.

[0135] The tertiary amine (iv) used in this paper is preferably of formula R 5 R 6 R 7 Compounds of N, where R 5 R 6 and R 7 Each can be independently substituted with an alkyl, alkenyl, aryl, aralkyl, or alkylaryl group.

[0136] R 5 R 6 and R 7 They can be the same or different. In some preferred embodiments, R 5 and R 6 Same, and R 7 different.

[0137] R 5 and R 6 Preferably, each of the components is an alkyl, alkenyl, aryl, aralkyl or alkylaryl group having 1 to 50 carbon atoms, more preferably 1 to 40 carbon atoms, and more preferably 1 to 30 carbon atoms, with optional substitutions.

[0138] R 5 and R 6 Each group may be optionally substituted with one or more groups selected from halogens (especially chlorine and fluorine), hydroxyl, alkoxy, ketone, acyl, cyano, mercapto, alkyl mercapto, dialkylamino, nitro, nitroso, and sulfoxide. The alkyl groups of these substituents may be further substituted.

[0139] R 5 and R 6 Preferably, each is an optionally substituted alkyl or alkenyl group. 5 and R 6 Preferably, each is an optionally substituted alkyl group. In some embodiments, R5 and R 6 Each of the optional substituted alkyl or alkenyl groups having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, suitably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, suitably 1 to 8 carbon atoms, for example 1 to 6 carbon atoms.

[0140] In some preferred embodiments, R 5 The substituted group preferably has 1 to 10, more preferably 1 to 4, alkyl or alkenyl groups. R is preferred. 5 It is an alkyl group. It can be a substituted alkyl group, such as a hydroxylated alkyl group. R is preferred. 5 It is an unsubstituted alkyl group. The alkyl chain can be straight or branched. R is preferred. 5 Selected from methyl, ethyl, propyl, and butyl, including their isomers. R is the most preferred. 5 It is a methyl group.

[0141] In some preferred embodiments, R 6 The substituted group preferably has 1 to 10, more preferably 1 to 4, alkyl or alkenyl groups. R is preferred. 6 It is an alkyl group. It can be a substituted alkyl group, such as a hydroxylated alkyl group. R is preferred. 6 It is an unsubstituted alkyl group. The alkyl chain can be straight or branched. R is preferred. 6 Selected from methyl, ethyl, propyl, and butyl, including their isomers. R is the most preferred. 6 It is a methyl group.

[0142] In some implementation schemes, R 7 The substituted groups are alkyl or alkenyl groups having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, suitably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, suitably 1 to 8 carbon atoms, for example 1 to 6 carbon atoms. Suitable substituents include halogens (especially chlorine and fluorine), hydroxyl groups, alkoxy groups, ketone groups, acyl groups, cyano groups, mercapto groups, alkyl mercapto groups, amino groups, alkylamino groups, nitro groups, nitroso groups, sulfoxide groups, amide groups, alkylamide groups, imide groups, and alkylimide groups. The alkyl groups of these substituents may be further substituted.

[0143] In some implementation schemes, R 7 The substituted group preferably has 1 to 10, more preferably 1 to 4, carbon atoms of alkyl or alkenyl groups. Suitablely, R 7 The alkyl group is optionally substituted. R is preferred. 7 The alkyl group is substituted. Preferred substituents include alkoxy and hydroxyl groups.

[0144] In some preferred embodiments, R7 The alkyl group is hydroxylated. The alkyl chain can be straight or branched. R is the most preferred. 7 It is hydroxyethyl.

[0145] Formula R 5 R 6 R 7 Suitable tertiary amine compounds of N include simple alkylamino and hydroxyalkylamino compounds; trialkylamino compounds with high molecular weight substituents; Mannich reaction products containing tertiary amines; and substituted acylated amines or alcohols containing tertiary amines.

[0146] Simple alkylamino and hydroxyalkylamino compounds are preferably of formula R 5 R 6 R 7 Compounds of N, where R 5 R 6 and R 7 Each is either alkyl or hydroxyalkyl. R 5 R 6 and R 7 They may be the same or different. In some implementations, R 5 R 6 and R 7 Each is independently selected from alkyl or hydroxyalkyl groups having 1 to 10, preferably 1 to 6, carbon atoms, for example 1 to 4 carbon atoms. R 5 R 6 and R 7 Each of these can be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl. Formula R 5 R 6 R 7 The amine of N can be a trialkylamine, a dialkylhydroxyalkylamine, a dihydroxyalkylalkylamine, or a trihydroxyalkylamine. There are many different compounds of this type, and these will be known to those skilled in the art.

[0147] In some implementation schemes, R 5 R 6 and R 7 One or two of the groups are short-chain alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms, and the other or two groups are longer-chain alkyl groups or groups having 6 to 30, preferably 10 to 24 carbon atoms.

[0148] In some implementation schemes, R 5 and R 6 Each is a C1 to C4 alkyl group, preferably methyl, and R 7 It is an alkyl or alkenyl group having 6 to 36, preferably 10 to 30, for example 12 to 24 carbon atoms.

[0149] Such compounds include, for example, dimethyloctadecylamine and hexadecyldimethylamine.

[0150] To provide quaternary ammonium compounds, hexadecyl dimethylamine can be quaternized by reacting it with propylene oxide (e.g., 1 to 3 molar equivalents of propylene oxide) and polyisobutylene succinic acid (e.g., 1 molar equivalent of polyisobutylene succinic acid).

[0151] For example, in some implementation schemes, R 5 It is a C1 to C4 alkyl group, preferably methyl, and R 6 and R 7 Each is an alkyl or alkenyl group having 6 to 36, preferably 8 to 30, for example 10 to 24 carbon atoms.

[0152] Such compounds include, for example, N,N-dimethylhexadecylamine, N-methyl-N,N-ditallowamine, and dicocarbamate.

[0153] Especially preferred formula R 5 R 6 R 7 N-tertiary amine compounds include N,N-dimethylethanolamine, N,N-dimethylhexadecylamine, dimethyloctadecylamine, and N-methylNN-ditallowamine.

[0154] In some embodiments, nitrogen-containing compounds having at least one tertiary amine group are (v) cyclic tertiary amines.

[0155] Suitable cyclic amines have the formula (D1): Where R 6 The substituted alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups are optionally substituted, and R 9 Together with N, it forms a heterocyclic ring.

[0156] The preferred heterocycle has fewer than 12 carbon atoms. R is preferred. 6 It has fewer than 8 carbon atoms.

[0157] Preferred R 6 It is an optionally substituted alkyl, alkenyl or aryl group having 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms.

[0158] R 6 It may be optionally substituted with one or more groups selected from halogens (especially chlorine and fluorine), hydroxyl, alkoxy, ketone, acyl, cyano, mercapto, alkyl mercapto, dialkylamino, nitro, nitroso, and sulfoxide. The alkyl groups of these substituents may be further substituted.

[0159] Preferred R 6 It can be an alkyl or alkenyl group that is optionally substituted. R is preferred.6 The alkyl group is optionally substituted. R is preferred. 6 It is an optionally substituted alkyl or alkenyl group having 1 to 7 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, suitably 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms.

[0160] Preferred R 6 The alkyl or alkenyl group is optionally substituted, and preferably has 1 to 6, more preferably 1 to 4, carbon atoms. R is preferred. 6 It is an alkyl group. It can be a substituted alkyl group, such as a hydroxylated alkyl group. R is preferred. 6 It is an unsubstituted alkyl or hydroxyalkyl group. More preferably, R 6 It is an unsubstituted alkyl group. The alkyl chain can be straight or branched. R is preferred. 6 Selected from methyl, ethyl, propyl, and butyl, including their isomers. R is the most preferred. 6 It is a methyl group.

[0161] In some implementation schemes, R 10 R 11 It forms an aromatic ring with N, and cyclic amines can have the structure (D2): In such implementations, group R 10 and R 11 The total number of carbon atoms in it is preferably less than 19.

[0162] R 9 Together with N, it can form aliphatic or aromatic heterocyclic groups. Thus, they form a heterocyclic ring. One or more additional heteroatoms may be present in the ring. Suitablely, the ring may contain one or more additional atoms selected from N, O, and S.

[0163] By R 9 The heterocyclic group formed with N may be substituted or unsubstituted; that is, one or more substituents may be present that are bonded to the atoms forming the ring. Suitable substituents include halogens (especially chlorine and fluorine); hydroxyl, alkoxy, ketone, acyl, cyano, mercapto, alkyl mercapto, alkyl, alkenyl, aryl, dialkylamino, alkylamino, nitro, nitroso, and sulfoxide. The alkyl, alkenyl, and aryl groups of these substituents may be further substituted.

[0164] This heterocyclic group can be replaced by another cyclic group, meaning it can be part of a bicyclic heterocyclic group.

[0165] In some preferred embodiments, N and R 9 The heterocyclic group formed was not substituted.

[0166] Preferred from R 9The group formed with N is a heterocyclic group having 3 to 12 atoms in the ring. The atoms in the ring include carbon atoms and other atoms. Preferably, the heterocyclic ring contains 3 to 10 atoms, more preferably 4 to 8, and more preferably 5 to 7 atoms.

[0167] In some preferred embodiments, the heterocyclic group contains only carbon and nitrogen atoms within the ring.

[0168] By R 9 The heterocyclic group formed with N can be aliphatic or aromatic.

[0169] In some preferred embodiments, R 9 Together with N, it forms an aliphatic or aromatic heterocycle with 5 to 7 atoms in the ring.

[0170] Suitable aliphatic heterocyclic groups include those based on pyrrolidine, piperidine, morpholine, and piperazine.

[0171] Suitable aliphatic heterocyclic groups include non-aromatic unsaturated heterocycles, i.e., those that may contain one or more double bonds, such as those based on dihydropyrrole.

[0172] Suitable aromatic heterocyclic groups include those based on pyrrole, pyridine, imidazole, pyrimidine, isoxazole, quinoline, oxazole, and pyrazole.

[0173] In a particularly preferred embodiment, R 9 Together with N, it forms an imidazole moiety or a pyrrolidine moiety.

[0174] Appropriately, R 9 It contains 3 to 11 carbon atoms (and optional heteroatoms in the ring), preferably 3 to 10 carbon atoms, more preferably 3 to 9 carbon atoms, suitably 3 to 8 carbon atoms, preferably 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms, for example 3 to 5 or 3 to 4 carbon atoms.

[0175] Preferred R 9 It contains fewer than 8 carbon atoms.

[0176] Compounds of formula (D1) or (D2) are cyclic tertiary amines. This is intended to mean that the nitrogen atom is part of a heterocyclic ring and preferably an amine group further bonded to another group.

[0177] Suitably, the compound of formula (D1) or (D2) is a cyclic tertiary amine having fewer than 18 carbon atoms. Preferably, it has fewer than 16 carbon atoms, suitably fewer than 14 carbon atoms, and most preferably fewer than 12 carbon atoms, for example, fewer than 10 carbon atoms, fewer than 8 carbon atoms, or fewer than 6 carbon atoms.

[0178] Suitablely, the cyclic amine compound is a compound of formula (D1) and is an N-substituted heterocyclic amine. Preferably, it is an N-alkyl heterocyclic amine having 5 to 7 atoms in the heterocyclic ring.

[0179] In some preferred embodiments, the tertiary amine is an N-methyl cyclic amine, wherein the heterocyclic ring moiety may contain one or more additional heteroatoms such as O, N or S, and may be aliphatic or non-aromatic.

[0180] There are many different compounds of this type, and these are known to those skilled in the art.

[0181] Some suitable cyclic amines used in this article are based on N-alkyl heterocycles, such as N-methyl heterocycles selected from pyrrolidine, piperidine, morpholine, piperazine, pyrrole, imidazole and dihydropyrrole.

[0182] Other suitable amines include those based on the above-described amines, wherein the heterocyclic ring contains one or more additional alkyl, alkenyl, or aryl substituents, provided that the total number of carbon atoms in the tertiary amine is less than 19. For example, compounds containing one, two, or three methyl groups bonded to carbon atoms within the heterocyclic ring are within the scope of this invention.

[0183] Some suitable cyclic amines used in this article include those based on heterocycles, where R 10 R 11 It forms an aromatic ring with N, such as those based on piperidine, pyrimidine, isoxazole, and oxazole.

[0184] Other suitable amines include those based on the above-mentioned amines, wherein the heterocyclic ring contains one or more additional alkyl, alkenyl, or aryl substituents, provided that the total number of carbon atoms in the tertiary amine is less than 19.

[0185] Tertiary amine compounds containing primary or secondary amine groups are within the scope of this invention, provided that these groups do not impede the quaternization of tertiary amines.

[0186] This cyclic tertiary amine compound preferably does not contain any free primary or secondary amine groups. Formula R 9 ==NR 6 Tertiary amine compounds may contain more than one tertiary amine group.

[0187] Some preferred cyclic amine compounds include 1-methylpyrrolidine, 1-methylimidazole, 1,2-dimethyl-1H-imidazole, pyridine, mixtures thereof, and isomers. 8-hydroxyquinoline may also be used.

[0188] Particularly preferred tertiary amine compounds include methylpyrrolidine and methylimidazole.

[0189] In some embodiments, nitrogen-containing compounds having at least one tertiary amine group are (vi) polyetheramine compounds.

[0190] Some preferred polyetheramine compounds are polyoxyalkyleneamines.

[0191] In some preferred embodiments, the polyetheramine compound has the general formula (D3): Where R 12 It is H or a hydrocarbon group having 1 to 30 carbon atoms; R 13 and R 14 Each is independently hydrogen or a lower alkyl group having about 1 to about 6 carbon atoms, and R 13 and R 14 In each --O---CHR 13 --CHR 14 --Each unit is selected independently; and x is an integer from 1 to 100, preferably from 5 to 50; A is NR 15 R 16 NR 17 NR 15 R 16 OR 17 NR 15 R 16 OCONR 15 R 16 Or a polyamine moiety having about 2 to about 12 nitrogen atoms, about 4 to about 40 carbon atoms and containing at least one tertiary amine group; wherein R 15 and R 16 Each is independently an alkyl group having about 1 to about 20 carbon atoms in each alkyl group, and R 17 It is an alkylene group having 1 to 20 carbon atoms.

[0192] In the preferred embodiment, R 12 For H or C1-C 30 Alkyl groups, preferably C4-C 20 alkyl.

[0193] In another preferred embodiment, R 12 It is an alkylphenyl group, wherein the alkyl group has about 1 to about 24 carbon atoms.

[0194] Preferably, R 13 and R 14 One of them is a lower alkyl group having 1 to 4 carbon atoms, and the other is hydrogen. More preferably, R 13 and R 14 One of them is methyl or ethyl, and the other is hydrogen.

[0195] R 15 and R 16Each is preferably an alkyl group having about 1 to about 20 carbon atoms in each alkyl group, more preferably about 1 to about 6 carbon atoms, and more preferably about 1 to about 4 carbon atoms. Suitably, R 17 The alkyl group having about 1 to about 20 carbon atoms in each alkyl group is preferred to have about 1 to about 6 carbon atoms, and more preferably about 1 to about 4 carbon atoms.

[0196] In some embodiments, A is a polyamine moiety containing a tertiary amine group and having about 2 to about 12 nitrogen atoms and about 4 to about 40 carbon atoms.

[0197] In some embodiments, compounds of formula (D3) can be derived by alkoxylation of N,N-dialkylhydroxyalkylamines such as N,N-dimethylaminoethanol or N,N-dimethylaminopropanol. In other embodiments, compounds of formula D4 can be derived by C1-C 30 alcohols (preferably C4-C) 20 The process involves the alkoxylation of an alcohol, followed by aminohydration, and then alkylation of the amine. This type of process is described in US2013225463.

[0198] Other preferred features of the polyetheramine compound are also described in US2013225463.

[0199] In a particularly preferred embodiment, the agglomerating additive of the present invention comprises a quaternary ammonium compound prepared by reacting a quaternary ammonium oxidizing agent with (i) a hydrocarbon-substituted acylation agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group.

[0200] The quaternary ammonium compounds used in this invention are prepared by reacting a nitrogen-containing compound having at least one tertiary amine group with a quaternizing agent.

[0201] Any compound that can react with tertiary amine groups to form quaternary ammonium cations can be used as a quaternizing agent.

[0202] In some embodiments, an ion exchange reaction can be carried out after reacting with a quaternizing agent to provide quaternary ammonium compounds with different anions.

[0203] The quaternary ammonium compounds used in this invention can be prepared by reacting a tertiary amine with a quaternizing agent selected from carboxylic acid esters, optionally combined with acids, epoxides, dialkyl sulfates, benzyl halides, hydrocarbon-substituted carbonates, alkyl halides, alkyl sulfonates, sulfonolactones, hydrocarbon-substituted phosphates, hydrocarbon-substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, or mixtures thereof.

[0204] In fuel applications, it is generally desirable to reduce levels of halogens, sulfur, and phosphorus compounds. Therefore, if quaternizing agents containing these elements are used, it may be advantageous to carry out subsequent reactions to exchange counterions. For example, quaternary ammonium compounds formed by reacting with alkyl halides can subsequently react with sodium hydroxide, and the sodium halide salt can be removed by filtration.

[0205] The quaternizing agent may include halides, such as chlorides, iodides, or bromides; hydroxides; sulfonates; bisulfites, alkyl sulfates, such as dimethyl sulfate; sulfones; phosphates; C1-12 alkyl phosphates; diC1-12 alkyl phosphates; borates; C1-12 alkyl borates; nitrites; nitrates; carbonates; bicarbonates; alkanoates; O,O-diC1-12 alkyl dithiophosphates; or mixtures thereof.

[0206] Preferably, the quaternizing agent is selected from carboxylic acid esters, dialkyl sulfates, benzyl halides, alkyl-substituted carbonates, alkyl-substituted epoxides optionally combined with acids, alkyl halides, alkyl sulfonates, sulfonyl lactones, alkyl-substituted phosphates, alkyl-substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or their salts, or mixtures thereof.

[0207] In one embodiment, the quaternizing agent may be derived from dialkyl sulfates such as dimethyl sulfate, N-oxides, sulfones such as propane and butane sulfone; alkyl, acyl, or aralkyl halides such as methyl and ethyl chlorides, bromides or iodides, or benzyl chlorides; and hydrocarbon (or alkyl)-substituted carbonates. If the quaternizing agent is benzyl chloride, the aromatic ring may optionally be further substituted with an alkyl or alkenyl group. The hydrocarbon (or alkyl) group of the hydrocarbon (or alkyl)-substituted carbonate may contain 1 to 50, 1 to 20, 1 to 10, or 1 to 5 carbon atoms per group. In one embodiment, the hydrocarbon-substituted carbonate contains two hydrocarbon groups that may be the same or different. Examples of suitable hydrocarbon-substituted carbonates include dimethyl or diethyl carbonates.

[0208] The preferred quaternizing agents used in this article are carboxylic acid esters or optional epoxides combined with acids.

[0209] In a preferred embodiment, the quaternizing agent is of formula R 18 COOR 19 Ester.

[0210] In such implementations, R 19 It is a C1 to C7 alkyl group, and R 18 COO is preferably a carboxylic acid residue selected from substituted aromatic carboxylic acids, α-hydroxycarboxylic acids, and polycarboxylic acids.

[0211] Preferred ester quaternizing agents are compounds of formula (E): Where R 18 The substituted alkyl, alkenyl, aryl, or alkylaryl groups may contain additional carboxyl-derived functional groups; and R 19 C1 to C 22 Alkyl, aryl, or alkylaryl.

[0212] The compounds of formula (E) are suitably carboxylic acid esters capable of reacting with tertiary amines to form quaternary ammonium compounds.

[0213] Suitable quaternizing agents include carboxylic acid esters with a pKa of 3.5 or lower.

[0214] The compound of formula (E) is preferably an ester of a carboxylic acid selected from substituted aromatic carboxylic acids, α-hydroxycarboxylic acids and polycarboxylic acids.

[0215] In some preferred embodiments, the compound of formula (E) is an ester of a substituted aromatic carboxylic acid, therefore R 18 To replace aryl groups.

[0216] In such implementations, R 18 Suitable for use is a substituted aryl group having 6 to 10 carbon atoms, preferably phenyl or naphthyl, with phenyl being the most preferred. 18 Appropriately selected from carboxyalkoxy, nitro, cyano, hydroxyl, SR 20 or NR 21 R 22 One or more groups are substituted. R 21 and R 22 Each can be hydrogen or optionally substituted alkyl, alkenyl, aryl, or carboxyalkoxy. R 21 and R 22 Each is preferably hydrogen or optionally substituted C1 to C2. 22 Alkyl groups, preferably hydrogen or C1 to C1. 16 Alkyl groups, preferably hydrogen or C1 to C1. 10 Alkyl, more preferably hydrogen or C1 to C4 alkyl. R is preferred. 21 It is hydrogen, and R 22 It is hydrogen or C1 to C4 alkyl. R is the most preferred. 21 and R 22 All are hydrogen. R is preferred. 18 It is an aryl group substituted with one or more groups selected from hydroxyl, carboxyalkoxy, nitro, cyano, and NH2. 18 It can be a polysubstituted aryl group, such as trihydroxyphenyl. R is preferred. 18 It is a monosubstituted aryl group. R is preferred. 18 For ortho-substituted aryl. Appropriately, R 18 It is substituted with a group selected from OH, NH2, NO2, or COOMe. R is preferred. 18 Replaced by an OH or NH2 group. Appropriately, R 18The aryl group is substituted with a hydroxyl group. The preferred option is R. 18 It is 2-hydroxyphenyl.

[0217] R 19 Preferably alkyl or alkylaryl. R 19 It can be C1 to C 16 Alkyl groups, preferably C1 to C2 10 Alkyl, preferably C1 to C8 alkyl. R 19 It can be C1 to C 16 Alkyl aryl, preferably C1 to C2 10 Alkyl, suitably C1 to C8 alkylaryl. R 19 It can be methyl, ethyl, propyl, butyl, pentyl, benzyl, or its isomers. R is preferred. 19 It is benzyl or methyl. R is the most preferred. 19 It is a methyl group.

[0218] Some particularly preferred compounds of formula (E) are salicylate esters, such as benzyl salicylate, methyl salicylate, ethyl salicylate, n- and isopropyl salicylate, and butyl salicylate.

[0219] The most preferred compound of formula (E) is methyl salicylate.

[0220] In some embodiments, the compound of formula (E) is an ester of an α-hydroxycarboxylic acid. In such embodiments, R 18 For R 23 CR 24 OH, and the compound of formula (E) has the following structure: Where R 23 and R 24 They may be the same or different, and each is selected from hydrogen, alkyl, alkenyl, aralkyl, or aryl. Such compounds applicable to this document are described in EP1254889.

[0221] Where R 18 Examples of compounds of formula (E) where COO is an α-hydroxycarboxylic acid residue include methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of 2-hydroxyisobutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of 2-hydroxy-2-methylbutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of 2-hydroxy-2-ethylbutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of lactic acid; and methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, benzyl, and allyl esters of glycolic acid. Of the above compounds, methyl 2-hydroxyisobutyrate is preferred.

[0222] In some embodiments, the compound of formula (E) is an ester of a polycarboxylic acid. In this definition, we mean including dicarboxylic acids and carboxylic acids having more than two acidic moieties.

[0223] In such implementations, R 18 It contains a carboxyl-derived functional group. This is preferably in the form of an ester, i.e., the R group. 18 One or more additional acid groups present in the ester are in esterified form. Preferred esters are C1 to C4 alkyl esters.

[0224] Compound (E) may be selected from diesters of oxalic acid, phthalic acid, maleic acid, malonic acid, or citric acid. A particularly preferred compound of formula (E) is dimethyl oxalate.

[0225] In a preferred embodiment, the compound of formula (E) is an ester of a carboxylic acid with a pKa less than 3.5. In such embodiments where the compound contains more than one acid group, we intend to refer to the first dissociation constant.

[0226] Compound (E) may be selected from an ester of a carboxylic acid selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid, and 2,4,6-trihydroxybenzoic acid.

[0227] Suitable, the compound of formula (E) may be selected from dimethyl oxalate, methyl 2-nitrobenzoate, dimethyl phthalate, dimethyl tartrate and methyl salicylate.

[0228] Preferred compounds of formula (E) include dimethyl oxalate, methyl 2-nitrobenzoate, and methyl salicylate.

[0229] The most preferred ester quaternizing agents are dimethyl oxalate and methyl salicylate.

[0230] In some preferred embodiments, the quaternizing agent is optionally an epoxide combined with an acid.

[0231] Any suitable epoxy compound can be used. Suitable epoxy compounds are those with the following formula: Where R 25 R 26 R 27 R 28 Each is independently selected from hydrogen or optionally substituted alkyl, alkenyl or aryl groups, provided that R 25 R 26 R 27 and R 28 At least one of them is hydrogen.

[0232] R 25 R 26 R 27 and R 28 At least two of them are preferably hydrogen. R 25 R 26 R 27 and R 28 The three most preferred are hydrogen. R 25 R 26 R 27 and R 28 It can be entirely composed of hydrogen.

[0233] In the above structure and subsequent constraints, R 25 and R 26 They are interchangeable, so either enantiomer or diastereomer can be used as component (b) when these groups are different.

[0234] In the above structure and subsequent constraints, R 27 and R 28 They are interchangeable, so either enantiomer or diastereomer can be used as component (b) when these groups are different.

[0235] R 25 Preferably, it is hydrogen or optionally substituted alkyl, alkenyl, aryl, alkylaryl, or aralkyl. 25 It can be appropriately selected from hydrogen and phenyl. R is the most preferred. 25 It is hydrogen.

[0236] R 26 Preferably, it is hydrogen-based or optionally substituted with alkyl, alkenyl, aryl, alkylaryl, or aralkyl groups. Most preferably, R... 26 It is hydrogen.

[0237] R 27 Preferably, it is hydrogen-based or optionally substituted with alkyl, alkenyl, aryl, alkylaryl, or aralkyl groups. Most preferably, R... 27 It is hydrogen.

[0238] R 28 Preferably, it is hydrogen or optionally substituted alkyl, alkenyl, aryl, alkylaryl or aralkyl.

[0239] In some preferred embodiments, R 28 The aryl group is optionally substituted. For example, R 28 It can be phenyl.

[0240] In some preferred embodiments, R 28 R is an optionally substituted alkyl or alkenyl group. 28 It can be an alkyl group, such as an unsubstituted alkyl group. R 28It can be an alkyl group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, suitably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, for example 1 to 8 or 1 to 4 carbon atoms.

[0241] In some implementation schemes, R 28 It is hydrogen.

[0242] In some implementation schemes, R 28 CH2OR 29 or CH2OCOR 30 Part, of which R 29 and R 30 Each can be optionally substituted alkyl, alkenyl, aryl, alkylaryl, or aralkyl.

[0243] R 29 Preferably, it is an optionally substituted alkyl or aryl group, preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, suitably 1 to 12 carbon atoms. When R 29 When it is an alkyl group, it can be linear or branched. In some embodiments, it is branched. R 29 The phenyl group may be optionally substituted.

[0244] In one implementation, R 29 It is 2-methylphenyl. In another embodiment, R... 29 It is CH2C(CH2CH3)CH2CH2CH2CH3.

[0245] R 30 It can be optionally substituted with alkyl, alkenyl, aryl, alkylaryl, or aralkyl groups.

[0246] R 30 Preferably, it is an optionally substituted alkyl or aryl group, preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, suitably 1 to 12 carbon atoms. When R 30 When it is an alkyl group, it can be linear or branched. In some preferred embodiments, it is branched. 30 The phenyl group may be optionally substituted.

[0247] In one implementation, R 30 It is C(CH3)R2, where each R is an alkyl group. The R groups may be the same or different.

[0248] R 30 Preferably, it is an alkyl group having 1 to 5 carbon atoms. In some embodiments, R 30 Oxygen atoms, i.e., R, can be included in the carbon chain. 30 It may contain ether functional groups.

[0249] Suitable epoxy compounds used as quaternizing agents in this article include ethylene oxide, propylene oxide, butane oxide, pentane oxide, hexane oxide, heptane oxide, dodecane oxide, alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether or isopropyl glycidyl ether, alkyl glycidyl esters, styrene oxide, stilbene oxide, and other C2 to C30 hydrocarbon groups.

[0250] Some preferred epoxy compounds used as quaternizing agents in this article include styrene oxide, ethylene oxide, propylene oxide, butane oxide, stilbene oxide, dodecane oxide, 2-ethylhexyl glycidyl ether, and isopropyl glycidyl ether. Styrene oxide, butane oxide, 2-ethylhexyl glycidyl ether, and propylene oxide are particularly preferred.

[0251] Typically, epoxide quaternizing agents are used in combination with acids. However, in embodiments where the nitrogen-containing class having at least one tertiary amine group includes (i) a reaction product of a substituted succinic acid (as an ester or amide) and also contains an additional unreacted carboxylic acid group, the additional acid can be omitted, and the hydrocarbon epoxide can be used alone as the quaternizing agent. It is believed that the formation of quaternary ammonium compounds is promoted by protonation of the carboxylic acid group also present in the molecule.

[0252] In such embodiments that do not use an additional acid, the quaternary ammonium compound is suitably prepared in a proton solvent. Suitable proton solvents include water, alcohols (including polyols), and mixtures thereof. Preferred proton solvents have a dielectric constant greater than 9.

[0253] In a preferred embodiment, the epoxide quaternizing agent is used in combination with an acid. Any suitable acid can be used. In a preferred embodiment, the acid is an organic acid, preferably a carboxylic acid. Suitable carboxylic acids include monocarboxylic acids and polycarboxylic acids. Preferably, the acid is a monocarboxylic acid or a dicarboxylic acid.

[0254] To avoid doubt, the acid appropriately activates the epoxide and forms an anionic counterion of the quaternary ammonium compound. In some embodiments, a subsequent ion exchange reaction may be carried out, but this is not preferred.

[0255] Any compound containing a carboxylic acid functional group can be used. In some embodiments, the acid can be a very small, simple molecule. Examples of suitable small-molecule simple acids include formic acid, acetic acid, propionic acid, and butyric acid.

[0256] In some implementations, the acid can be a simple fatty acid compound. However, the acid can also be a more complex molecule containing additional acid functional groups.

[0257] Suitable fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ceric acid, ceric acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, transoleic acid, isoleic acid, linoleic acid, isolinic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, undecenoic acid, and docosahexaenoic acid.

[0258] Suitable complex acids include substituted phthalic acid and succinic acid derivatives.

[0259] Some preferred types of these are hydrocarbon-substituted phthalic acid or succinic acid derivatives. Hydrocarbon-substituted succinic acid derivatives are particularly preferred.

[0260] In one embodiment, the hydrocarbon group is preferably polyisobutylene-based, preferably having a molecular weight of 100 to 5000, more preferably 300 to 4000, suitably 450 to 2500, for example 450 to 2000 or 450 to 1500.

[0261] In one embodiment, the hydrocarbon group is an alkyl or alkenyl group having 6 to 30 carbon atoms, preferably 10 to 26 carbon atoms, more preferably 12 to 24 carbon atoms, suitably 16 to 20 carbon atoms, for example 18 carbon atoms.

[0262] In one embodiment, the hydrocarbon group is an alkyl or alkenyl group having 6 to 50 carbon atoms, preferably 12 to 40 carbon atoms, more preferably 18 to 36 carbon atoms, suitably 24 to 36 carbon atoms, for example 30 carbon atoms.

[0263] This succinic acid derivative can be polyisobutylene succinic acid (e.g., it can be used with epoxide quaternizing agents such as propylene oxide). Polyisobutylene succinic acid can form salts through one or two of its acid groups. When only one of its acid groups is used to form a salt, it can retain a free acid group.

[0264] In embodiments where the acid has more than one acid functional group, the additional groups may be present in the form of a free acid or an ester. When more than one free acid group is present, an equal amount of cations may also be present. For example, in some embodiments, the quaternary ammonium compound may comprise a dicarboxylate dianion and two quaternary ammonium ions. Such compounds are described in EP3024913.

[0265] Some preferred epoxide quaternizing agents used in this article include styrene oxide, epoxide butane, epoxide propylene oxide, or 2-ethylhexyl glycidyl ether, used in combination with monocarboxylic acids (suitably acetic acid).

[0266] Some preferred epoxide quaternizing agents used in this article include styrene oxide, epoxide, propylene oxide, or 2-ethylhexyl glycidyl ether, used in combination with polycarboxylic acids (appropriately polyisobutylene-substituted succinic acid).

[0267] In some preferred embodiments, the quaternizing agent is selected from carboxylic acid esters, quaternizing agents optionally combined with acids, and chloroacetic acid or its salts.

[0268] In some preferred embodiments, the agglomerating additive of the present invention comprises a quaternary ammonium compound, which is of formula R 5 R 6 R 7 Tertiary amines of N-tertiary amines (where R) 5 R 6 and R 7 Each is an independently substituted alkyl or alkenyl group having 1 to 40 carbon atoms, an epoxide, or a monocarboxylic or dicarboxylic acid reaction product.

[0269] In some embodiments, the agglomerating additive of the present invention comprises a quaternary ammonium compound, which is of formula R 5 R 6 R 7 Tertiary amines of N-tertiary amines (where R) 5 R 6 and R 7 Each of the following is a reaction product consisting of an alkyl or hydroxyalkyl group having 1 to 10 carbon atoms, an epoxide, and a monocarboxylic acid or dicarboxylic acid.

[0270] In some embodiments, the agglomerating additive of the present invention comprises a quaternary ammonium compound, which is of formula R 5 R 6 R 7 Tertiary amines of N-tertiary amines (where the group R) 5 R 6 and R 7 One or two of them are short-chain alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms, and the other or two groups are longer-chain alkyl groups or groups having 6 to 30, preferably 10 to 24 carbon atoms, epoxides, and reaction products of monocarboxylic acids or dicarboxylic acids.

[0271] In some embodiments, the agglomerating additive of the present invention comprises a quaternary ammonium compound, which is a tertiary amine, an epoxide (preferably propylene oxide), and optionally substituted succinic acid (preferably polyisobutylene-substituted succinic acid, wherein the tertiary amine has the formula R). 5 R 6 R 7 N, where the group R 5 R 6 and R 7The reaction product is composed of one or two short-chain alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms, and the other or two groups being longer-chain alkyl groups or groups having 6 to 30, preferably 10 to 24 carbon atoms.

[0272] The preferred agglomerating additive used in this invention comprises at least one quaternary ammonium compound, which is a reaction product of the following substances: (x) The reaction product of a hydrocarbon-substituted acylated agent and a compound having at least one tertiary amine group and a primary amine, secondary amine, or alcohol group; and (y) is selected from the following quaternizing agents: carboxylic acid esters; and optionally epoxides in combination with acids.

[0273] The preferred agglomerating additive used in this invention comprises at least one quaternary ammonium compound, which is a reaction product of the following substances: (x) The reaction product of a hydrocarbon-substituted succinic acid-derived acylating agent comprising an average of at least 1.2 succinic acid moieties per molecule and a compound having at least one tertiary amine group and a primary amine, secondary amine, or alcohol group; and (y) is selected from the following quaternizing agents: carboxylic acid esters; and optionally epoxides in combination with acids.

[0274] A more preferred agglomerating additive used in this invention comprises at least one quaternary ammonium compound, which is a reaction product of the following substances: (x) a polyisobutylene-substituted succinic acid or its anhydride and an amine or alcohol further comprising a tertiary amine group; and (y) A quaternizing agent selected from the following: esters of one or more carboxylic acids selected from oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenic acid, aminobenzoic acid and 2,4,6-trihydroxybenzoic acid; and epoxides selected from one or more of ethylene oxide, propylene oxide, butane oxide, pentane oxide, hexane oxide, heptane oxide, isopropyl glycidyl ether, styrene oxide, stilbene oxide and other C2 to C30 hydrocarbon groups, optionally in combination with an acid.

[0275] Some particularly preferred agglomerating additives used in this invention comprise at least one quaternary ammonium compound, which is a reaction product of the following substances: (x) a polyisobutylene-substituted succinic acid or its anhydride having a PIB molecular weight of 170 to 2800, preferably 450 to 1500, and an amine or alcohol selected from dimethylaminopropanol, dimethylaminopropylamine, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, or combinations thereof; and (y) is a quaternizing agent selected from the following: dimethyl oxalate, methyl 2-nitrobenzoate, dimethyl phthalate, dimethyl tartrate, methyl salicylate; and epoxides selected from styrene oxide, 2-ethylhexyl glycidyl ether, ethylene oxide, propylene oxide, butane oxide, 2-ethylhexyl glycidyl ether, stilbene oxide and isopropyl glycidyl ether in combination with an acid.

[0276] Some particularly preferred agglomerating additives used in this invention comprise at least one quaternary ammonium compound, which is a reaction product of the following substances: (x) a polyisobutylene-substituted succinic acid or its anhydride having a PIB molecular weight of 170 to 2800, preferably 450 to 1500, and an amine or alcohol selected from dimethylaminopropanol and dimethylaminopropylamine; and (y) is selected from the following quaternizing agents: dimethyl oxalate; methyl salicylate; and epoxides selected from styrene oxide, propylene oxide and butane oxide in combination with acids.

[0277] Some particularly preferred agglomerating additives used in this invention comprise at least one quaternary ammonium compound, which is a reaction product of the following substances: (x) A polyisobutylene-substituted succinic acid or its anhydride having a PIB molecular weight of 170 to 2800, preferably 450 to 1500, and comprising an average of at least 1.2 succinic acid moieties per molecule and an amine or alcohol selected from dimethylaminopropanol and dimethylaminopropylamine; and (y) is selected from the following quaternizing agents: dimethyl oxalate; methyl salicylate; and epoxides selected from styrene oxide, propylene oxide and butane oxide in combination with acids.

[0278] In some embodiments, the agglomerating additive may comprise the quaternization reaction product of a fatty acid (e.g., oleic acid) and dimethylaminopropylamine. For example, the agglomerating additive may comprise the reaction product of oleic acid or its reactive equivalent and dimethylaminopropylamine quaternized by reaction with chloroacetic acid or a salt thereof.

[0279] In some embodiments, the agglomerating additive may comprise at least one quaternary ammonium compound, which is a reaction product of dimethylhexadecylamine, propylene oxide, and polyisobutylene-substituted succinic acid. In a preferred embodiment, the succinic acid has polyisobutylene substituents with a number average molecular weight of 450 to 1500.

[0280] This invention relates to the use of gasoline fuel compositions.

[0281] The term "gasoline" refers to a liquid fuel (usually or preferably primarily or solely composed of C4-C12 hydrocarbons) used in spark-ignition engines and that meets international gasoline specifications such as ASTM D-439 and EN228. This term includes blends of distillate hydrocarbon fuels with oxygen-containing components such as alcohols or ethers (e.g., methanol, ethanol, butanol, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE)), as well as the distillate fuel itself.

[0282] The inventors have surprisingly discovered that even very low concentrations of quaternary ammonium compounds can significantly agglomerate nanoparticles emitted by direct-injection spark ignition engines.

[0283] Suitablely, the agglomerating additive is present in the gasoline fuel composition in an amount of less than 300 ppm, suitablely less than 100 ppm, preferably less than 50 ppm, and most preferably less than 30 ppm. In some embodiments, the agglomerating additive is present in the gasoline fuel composition in an amount of less than 20 ppm, preferably less than 15 ppm, most preferably less than 10 ppm, for example less than 8 ppm or even less than 5 ppm.

[0284] Suitable, the agglomerating additive is present in the gasoline fuel composition in an amount of 0.1 to 100 ppm, preferably 0.5 to 50 ppm, preferably 1 to 25 ppm or 1 to 10 ppm.

[0285] In this specification, any reference to ppm refers to parts per million by weight.

[0286] The gasoline fuel composition used in this invention may comprise a mixture of two or more quaternary ammonium compounds as agglomerating additives. In such embodiments, the above-mentioned amounts refer to the total amount of all such compounds present in the composition.

[0287] Those skilled in the art will understand that commercial sources of additives may include diluents or carriers. All quantities mentioned herein refer to the amount of the active quaternary ammonium compound.

[0288] This agglomerating additive contains one or more quaternary ammonium compounds.

[0289] The amounts of agglomerating additives mentioned herein refer to the total amount of active quaternary ammonium compounds present in the composition. The amounts mentioned herein do not include any diluents or carriers, nor any unreacted starting materials or byproducts. However, such components may be present in additive compositions added to fuels. The crude reaction mixture following the quaternization reaction can be used as an additive without purification, but the amounts mentioned herein refer to one or more active quaternary ammonium compounds.

[0290] The use of mixtures may be due to the availability of starting materials, or it may be a deliberate choice to use a particular mixture to obtain benefits. For example, a particular mixture may lead to improved processing, improved overall performance, or improved synergistic performance.

[0291] In some preferred embodiments, the agglomerating additive can be used without additional components. In other preferred embodiments, the agglomerating additive is used with one or more additional components selected from the following: a) Carrier oil b) Acyl nitrogen compounds, which are the reaction products of carboxylic acid-derived acylating agents and amines. c) Hydroxyl-substituted amines, wherein the alkyl substituents are primarily aliphatic and contain at least 8 carbon atoms. d) Mannich base additives comprising nitrogen-containing condensates of phenols, aldehydes, and primary or secondary amines; and e) Polyetheramine.

[0292] Such additional components are well known to those skilled in the art. Suitable additives of this kind are described, for example, in WO 2019 / 186125.

[0293] Preferably, the agglomerating additive and other additives (if present) are present in the fuel in the fuel storage tank supplied to the engine. Although they may be mixed into the fuel in the storage tank, it is preferred that they are present in the bulk fuel pumped into the storage tank.

[0294] This agglomerate additive can be added to gasoline fuel at any convenient point in the supply chain. For example, it can be added to fuel at the refinery, distribution terminal, or after the fuel has left the distribution terminal. If the agglomerate additive is added to fuel after it has left the distribution terminal, this is called an aftermarket application. Aftermarket applications include situations such as adding the additive to fuel in delivery tank trucks, adding it directly to a customer's bulk storage tank, or adding it directly to the end user's vehicle tank. Aftermarket applications may include supplying fuel additives in vials suitable for direct addition to fuel storage tanks or vehicle tanks.

[0295] This invention provides a method and application for agglomerating nanoparticles in the exhaust stream generated by the combustion of a gasoline fuel composition in a direct-injection spark ignition engine.

[0296] Agglomerated nanoparticles refer to nanoparticles that combine together to form larger particles.

[0297] Nanoparticles are particles having one or more sizes on the order of 100 nm or smaller. The size of nanoparticles can be measured by any suitable method. For example, any method described in British Standard PAS 71:2005 can be used. Preferred methods for determining particle size include TEM (transmission electron microscopy, when the particles are made of a material with high contrast to a carbon TEM grid), SEM (scanning electron microscopy), and AFM (atomic force microscopy). If the particles exhibit plasmon resonance, the size can also be determined from peaks in the UV-VIS spectrum. For particles on the order of 100 nm... -8 Larger particles, such as those in the meter range or larger, can be scattered using light. In some embodiments, the methods and uses of the present invention reduce the emission of nanoparticles with a particle size (as defined above) of 5 nm to 100 nm, for example, 10 nm to 80 nm.

[0298] The emission of nanoparticles poses a unique hazard. These particles are known to be most harmful to human health and the environment. Therefore, agglomerating nanoparticles into larger particles can provide particles that are less hazardous and more easily captured by filters.

[0299] A preferred method for measuring particulate matter emissions is described in the examples. The size, quantity, and distribution of the emitted particulate matter are appropriately measured using a Cambustion® DMS500 exhaust gas analyzer equipped with a catalytic stripping attachment (CSA) via an electromobility detection method.

[0300] The method and application of the present invention appropriately reduce the emission of nanoparticles from direct injection spark ignition engines.

[0301] Preferably, the method and application of the present invention reduce the amount of nanoparticles emitted by a direct injection spark ignition engine by at least 50%. Preferably, the method and application of the present invention reduce the amount of nanoparticles (preferably with a diameter of 1 to 100 nm) emitted by a direct injection spark ignition engine by at least one order of magnitude. Preferably, the concentration of nanoparticles (preferably with a diameter of 1 to 100 nm) emitted by a direct injection spark ignition engine is reduced by at least tenfold.

[0302] In the method and application of this invention, nanoparticles agglomerate to form larger particles. Therefore, the resulting particles are larger in size but fewer in number.

[0303] Appropriately, the present invention reduces the total number of particulate matter emitted per unit volume of exhaust gas.

[0304] Appropriately, the present invention reduces the number of nanoparticles emitted per unit volume of exhaust gas.

[0305] In addition to reducing the number of emitted nanoparticles and the total number of emitted particulate matter, the present invention preferably also reduces the total mass of all particulate matter emitted per unit volume of exhaust gas.

[0306] Appropriately, the present invention reduces the total mass and total number of all particulate matter emitted per unit volume of exhaust gas.

[0307] One particular advantage of this invention is the reduction in emissions of nanoparticles small enough to pass through exhaust filters.

[0308] This invention agglomerates nanoparticles emitted by direct-injection spark-ignition engines. In some embodiments, exhaust gases from the engine can be directed through a particulate filter. In such embodiments, this invention can advantageously increase the number of particles captured by the filter in the exhaust stream.

[0309] Appropriately, the method and use of the present invention reduce the number of nanoparticles per unit volume passing through a gasoline particulate filter.

[0310] Therefore, the present invention can provide the use of one or more quaternary ammonium compounds as agglomerating additives in gasoline fuel compositions to improve the performance of particulate filters installed in the exhaust of direct injection spark-ignition engines, wherein the performance improvement involves reducing the mass of particulate matter passing through the filter during combustion of the gasoline fuel composition.

[0311] In some embodiments, the present invention may provide a method for increasing the mass of particulate matter captured by a gasoline particulate filter installed in the exhaust flow of a direct-injection spark-ignition engine, the method comprising adding an agglomerating additive comprising one or more quaternary ammonium compounds to a gasoline fuel composition.

[0312] In some embodiments, the present invention may provide a method for handling nanoparticles in the exhaust stream generated by the combustion of a gasoline fuel composition in a cohesive direct injection spark ignition engine, the method comprising the following steps: - To prepare a gasoline fuel composition comprising one or more quaternary ammonium compounds as agglomerating additives; - Combustion of the gasoline fuel composition in a direct injection spark ignition engine; and - Measure the particulate matter size emitted from engine exhaust during combustion of a gasoline fuel composition containing agglomerating additives.

[0313] In some embodiments, the method may further include comparing the particulate size distribution of engine exhaust emissions during combustion of a gasoline fuel composition containing an agglomerating additive with the particulate size distribution of engine exhaust emissions during combustion of a gasoline fuel composition without an agglomerating additive. The gasoline fuel composition without an agglomerating additive is suitably a fuel composition otherwise identical.

[0314] This invention relates to nanoparticles in the exhaust stream generated by the combustion of gasoline fuel in agglomerated direct injection spark ignition engine. Appropriately, agglomeration causes a shift in the size distribution of the emitted particles, resulting in an increase in the average particle size.

[0315] In some embodiments, the present invention can provide a reduction in the number of particles with an average diameter less than 100 nm per unit volume of exhaust gas emission, and an increase in the number of particles with an average diameter greater than 100 nm per unit volume of exhaust gas emission. Particle size is appropriately measured according to the method used in the embodiments.

[0316] In an embodiment of a direct-injection spark-ignition engine where the exhaust flow passes through a gasoline particulate filter, the method may involve measuring the size of particles in the exhaust flow before and after passing through the gasoline particulate filter.

[0317] It is preferable to reduce the number of nanoparticles per unit volume of exhaust flow before they pass through the gasoline particulate filter.

[0318] It is preferable to reduce the mass of particulate matter passing through the gasoline particulate filter.

[0319] In a particularly preferred embodiment, the present invention provides the use of an agglomerating additive comprising 1 to 20 ppm of one or more quaternary ammonium compounds in a gasoline composition for agglomerating nanoparticles in the exhaust stream generated by combustion of a gasoline fuel composition in a direct-injection spark-ignition engine, wherein the quaternary ammonium compound is a quaternization reaction product of an acylation agent derived from a hydrocarbon-substituted succinic acid and a compound comprising at least one tertiary amine group and a primary amine, secondary amine, or alcohol group, wherein the hydrocarbon-substituted acylation agent comprises an average of at least 1.2 succinic acid moieties per molecule.

[0320] In a preferred embodiment, the present invention provides the use of an agglomerating additive comprising 1 to 100 ppm, preferably 1 to 50 ppm, of one or more quaternary ammonium compounds in a gasoline composition for agglomerating nanoparticles in the exhaust stream generated by combustion of a gasoline fuel composition in a direct injection spark ignition engine, wherein the quaternary ammonium compound is a reaction product of dimethylhexadecylamine, propylene oxide, and polyisobutylene-substituted succinic acid.

[0321] In a preferred embodiment, the present invention provides the use of an agglomerating additive comprising 1 to 100 ppm, preferably 1 to 50 ppm, of one or more quaternary ammonium compounds in a gasoline composition for agglomerating nanoparticles in the exhaust stream generated by combustion of a gasoline fuel composition in a direct-injection spark-ignition engine, wherein the quaternary ammonium compound is a reaction product of oleic acid or its reactive equivalent and dimethylaminopropylamine by reacting with chloroacetic acid or its salt.

[0322] The invention will now be further described through the following non-limiting examples. In the following examples, the processing rate values ​​given in parts per million (ppm) represent the amount of surfactant, rather than the amount of added formulation (containing surfactant). All ppm are by weight.

[0323] Example 1 Intermediate additive A (the reaction product of a hydrocarbon-substituted acylation agent and a compound of formula (B1)) is prepared as follows: Add 554.36 g (0.467 mol) of PIBSA (made from 1000 molecular weight PIB and maleic anhydride) to a 1-liter container. Stir and heat the mixture to 120°C under nitrogen atmosphere. Add 47.72 g (0.467 mol) of DMAPA over 1 hour, and heat the mixture to 140°C and maintain for 3 hours while removing water using a Dean-Stark apparatus.

[0324] [Note: PIB here refers to polyisobutylene; PIBSA refers to polyisobutylene-substituted succinic anhydride; DMAPA refers to dimethylaminopropylamine] Example 2 Additive B (an additive containing the quaternary ammonium compound of the present invention) is prepared as follows: 333.49 g (0.262 mol) of Additive A was mixed with 39.92 g (0.262 mol) of methyl salicylate under nitrogen atmosphere. The mixture was stirred and heated to 140 °C and maintained for 8 hours. The content of non-volatile contents was adjusted to 60% w / w using Caromax 20. The product mixture of this reaction was used as Additive B without further processing and contained quaternary ammonium compounds as well as any unreacted raw materials, other reaction products, and solvents.

[0325] Example 3 Additive C (an additive containing the quaternary ammonium compound of the present invention) is prepared as follows: 700 grams (0.7 mol) of polyisobutylene (M n1000) was added to a nitrogen-purged jacketed reactor equipped with a top stirrer. The starting material was heated to 120°C with stirring and repeatedly inertized with nitrogen. The reaction temperature was raised to 190°C, and maleic anhydride (82.4 g, 0.84 mol, 1.2 equivalents) was added over 1 hour. After maintaining the temperature at 190°C for another hour, the temperature was raised to 200-208°C and maintained within this range for 8 hours. Then, a vacuum (<30 mbar) was applied for 2.5 hours while maintaining the reaction temperature, reducing the residual maleic anhydride content to ≤0.05% by weight. The reactants were cooled to ≤80°C and then discharged from the reactor. The resulting PIBSA was added to a nitrogen-purged jacketed reactor equipped with a top stirrer and heated to 120°C. 3-(dimethylamino)propylamine (DMAPA) (1 equivalent relative to the anhydride group) was slowly added, maintaining the reaction temperature between 120-130°C. After stirring at 120°C for another hour, the reaction temperature was raised to 140°C and maintained for 3 hours, while distilling water was added. Methyl salicylate (2.1 equivalents relative to the anhydride group) was added in one go, and heating was continued at 140°C for 10 hours. The reactants were diluted with Aromatic 150 solvent to provide a total solids content of 60% by weight before being discharged from the reactor.

[0326] Example 4 A gasoline composition containing additive C (30 mg / kg additive treatment rate) was prepared and added to equal aliquots taken from a common batch of base fuel. This base fuel conforms to EN228 and its specifications are shown in Table 1.

[0327] Table 1 .

[0328] Example 5 - Particulate Matter Emission Measurement The size, quantity, and distribution of particulate matter emissions are measured using the Cambustion® DMS500 exhaust gas analyzer equipped with a Catalytic Stripping Attachment (CSA). This instrument uses an electromobility detection method to measure particulate matter ranging in size from 5 to 1000 nm.

[0329] For direct injection spark ignition (DISI) engines equipped with gasoline particulate filters (GPF), two DMS500 instruments are used to measure the size, quantity, and distribution of emitted particulate matter before and after the GPF.

[0330] The following procedure should be used to evaluate the ability of the claimed additive to reduce particulate matter emissions with a size of 10 to 1000 nm.

[0331] A 2.0-liter turbocharged gasoline direct injection (GDI) engine compliant with Euro 6 standards was connected to an automated testing system and test bench equipped with an engine dynamometer. The engine was controlled by an ECU provided by the engine manufacturer. The engine configuration included a gas permeable powder (GPPF), and particulate emissions were measured before and after the GPF (as described above).

[0332] The test cycle is 48 hours and consists of a single speed and load point (42% load at 2000 RPM).

[0333] The base fuel is specified in Table 1. The test fuel contains 30 ppm of additive C.

[0334] The engine test results are shown in Table 2. In Table 2, the term "total particulate matter average" refers to the average value taken over the entire 48-hour test and includes all particulate matter measured within the specified size range.

[0335] Table 2 .

[0336] Example 6 Additive D (a quaternary ammonium compound) was prepared by quaternizing hexadecyl dimethylamine with 2 equivalents of propylene oxide in the presence of polyisobutylene succinic acid (having a PIB number-average molecular weight of 1000), as described in the general synthesis method of WO2014 / 195464 and Example 6. The resulting material, as a solution, contained 60% by weight of the active ingredient.

[0337] 30 ppm of active additive D was added to the base fuel conforming to the specifications described in Table 1, and the test was performed according to the procedure described in Example 5. The results are shown in Table 3. In Table 3, the term "total particulate matter average" refers to the average value taken over the entire 48-hour test and includes all particulate matter measured within the specified size range.

[0338] Table 3 .

Claims

1. A method for agglomerating nanoparticles in the exhaust stream generated by the combustion of a gasoline fuel composition in a direct-injection spark ignition engine, the method comprising adding one or more quaternary ammonium compounds as agglomerating additives to the gasoline fuel composition.

2. Use of one or more quaternary ammonium compounds as agglomerating additives in gasoline fuel compositions for agglomerating nanoparticles in the exhaust stream generated by combustion of the gasoline fuel composition in a direct-injection spark-ignition engine.

3. The method or use according to claim 1 or 2, wherein the quaternary ammonium compound, or each quaternary ammonium compound, is a reaction product of a nitrogen-containing compound having at least one tertiary amine group and a quaternizing agent, wherein the nitrogen-containing compound having at least one tertiary amine group may be selected from: (i) The reaction product of a hydrocarbon-substituted acylated agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group; (ii) Mannich reaction products containing tertiary amine groups; (iii) A polyalkylene-substituted amine having at least one tertiary amine group; (iv) Equation R 5 R 6 R 7 N-tertiary amines, where R 5 R 6 and R 7 Each can be independently substituted with an alkyl, alkenyl, aryl, alkylaryl, or aralkyl group; (v) cyclic tertiary amines; and (vi) Polyetheramine compounds.

4. The method or use according to claim 3, wherein the nitrogen-containing compound having at least one tertiary amine group is a reaction product of an alcohol or amine containing a tertiary amino group and optionally a substituted succinic acid or its anhydride.

5. The method or use according to claim 4, wherein the succinic acid or its anhydride is substituted with a hydrocarbon group, and the hydrocarbon-substituted acylated agent comprises an average of at least 1.2 succinic acid moieties per molecule.

6. The method or use according to claim 4 or 5, wherein the succinic acid or its anhydride is substituted with a polyisobutylene group having a number average molecular weight of 170 to 2800, preferably 450 to 1500.

7. The method or use according to any one of claims 3 to 6, wherein the alcohol or amine containing the tertiary amino group is selected from dimethylaminopropanol, dimethylaminopropylamine, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, or combinations thereof.

8. The method or use according to any one of claims 3 to 7, wherein the quaternizing agent is selected from carboxylic acid esters, dialkyl sulfates, benzyl halides, alkyl-substituted carbonates, optionally alkyl-substituted epoxides in combination with acids, alkyl halides, alkyl sulfonates, sulfonyl lactones, alkyl-substituted phosphates, alkyl-substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or salts thereof, or mixtures thereof.

9. The method or use according to claim 8, wherein the quaternizing agent is of formula R 18 COOR 19 esters, in which R 19 It is a C1 to C7 alkyl group, and R 18 It is a residue of a carboxylic acid selected from substituted aromatic carboxylic acids, α-hydroxycarboxylic acids, and polycarboxylic acids.

10. The method or use according to claim 9, wherein the quaternizing agent is an ester of one or more carboxylic acids selected from oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid, and 2,4,6-trihydroxybenzoic acid.

11. The method or use according to claim 10, wherein the quaternizing agent is selected from dimethyl oxalate, methyl 2-nitrobenzoate, dimethyl phthalate, dimethyl tartrate, and methyl salicylate.

12. The method or use according to claim 8, wherein the quaternizing agent is selected from epoxides optionally combined with an acid, wherein the epoxide has the following formula: Where R 25 R 26 R 27 R 28 Each is independently selected from hydrogen or optionally substituted alkyl, alkenyl or aryl groups, provided that R 25 R 26 R 27 and R 28 At least one of them is hydrogen.

13. The method or use according to claim 12, wherein R 25 R 26 and R 27 Each is hydrogen, and R 28 Selected from phenyl, optionally substituted alkyl or alkenyl groups having 1 to 20 carbon atoms, hydrogen, CH2OR 29 or CH2OCOR 30 , where R 29 and R 30 Each is an alkyl or aryl group with 1 to 20 carbon atoms, which are optionally substituted.

14. The method or use according to claim 13 or 14, wherein the epoxide is selected from styrene oxide, ethylene oxide, propylene oxide, butane oxide, stilbene oxide, and isopropyl glycidyl ether.

15. The method or use according to any one of claims 8, 12, 13 or 14, wherein the epoxide quaternizing agent is used in combination with an acid.

16. The method or use according to claim 15, wherein the acid is selected from: - Simple small-molecule acids selected from formic acid, acetic acid, propionic acid and butyric acid; - Fatty acid compounds; and - Hydrocarbon-substituted phthalic acid or succinic acid derivatives.

17. The method or use according to any one of the preceding claims, wherein the gasoline composition further comprises one or more additional components selected from: a) Carrier oil b) Acyl nitrogen compounds, which are the reaction products of carboxylic acid-derived acylating agents and amines. c) Hydroxyl-substituted amines, wherein the hydrocarbon substituents are primarily aliphatic and contain at least 8 carbon atoms. d) Mannich base additives comprising nitrogen-containing condensates of phenols, aldehydes, and primary or secondary amines; and e) Polyetheramine.

18. The method or use according to any one of the preceding claims reduces the number of particulate matter emitted per unit volume of exhaust gas and / or the total mass of particulate matter emitted per unit volume of exhaust gas.

19. The method or use according to any one of the preceding claims reduces the number of particulate matter emitted per unit volume of exhaust gas and / or the total mass of particulate matter emitted per unit volume of exhaust gas by at least 50%.

20. The method or use according to any one of the preceding claims, wherein the agglomerating additive is present in the gasoline composition in an amount of 0.5 to 50 ppm.

21. A method for detecting nanoparticles in the exhaust stream generated during the combustion of a gasoline fuel composition in a cohesive direct injection spark ignition engine, the method comprising the following steps: - To prepare a gasoline fuel composition comprising one or more quaternary ammonium compounds as agglomerating additives; - Combustion of the gasoline fuel composition in a direct injection spark ignition engine; and - Measure the particulate matter size emitted from engine exhaust during combustion of a gasoline fuel composition containing the agglomerating additive.

22. The method of claim 21, further comprising the step of comparing the size distribution of particulate matter emitted from engine exhaust during combustion of a gasoline fuel composition containing an agglomerating additive with the micron-sized distribution of particulate matter emitted from engine exhaust during combustion of a gasoline fuel composition without an agglomerating additive.

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