Compositions and methods for preventing or reducing low-speed pre-ignition in spark-ignition internal combustion engines

Abstract

Fuel and lubricant compositions containing a low speed primary pre-ignition (LSPI) reducing additive are provided, including (i) an amino additive, (ii) an amine additive, (iii) a triazole additive, (iv) a benzamidinium additive, (v) a benzoxazole additive, or (vi) an N=CX motif additive. Methods for preventing or reducing low speed pre-ignition events in spark ignition engines using these compositions are also provided.

Description

[Technical Field]

[0001] Technical field This disclosure relates to fuel and lubricant compositions for spark-ignition engines, and to methods for using them to prevent or reduce low-speed pre-ignition events. [Background technology]

[0002] background Turbocharged or supercharged engines (i.e., boosted internal combustion engines) may exhibit abnormal combustion phenomena known as stochastic pre-ignition or slow pre-ignition (or "LSPI"). LSPI is a set of events that may include very high pressure spikes, premature combustion at improper crank angles, and knocking. All of these, individually or in combination, can cause engine degradation or serious damage. However, because LSPI events occur only sporadically and uncontrollably, identifying the cause of this phenomenon and developing solutions to suppress it is difficult.

[0003] Pre-ignition is a form of combustion that causes the air-fuel mixture (air-fuel mixture) in the combustion chamber to ignite before the desired ignition by the ignition system. Pre-ignition is usually a problem when running a high-load engine because the heat from the engine's operation can heat a portion of the combustion chamber to a temperature sufficient to ignite the mixture upon contact. This type of pre-ignition is sometimes called hot-spot pre-ignition.

[0004] More recently, intermittent abnormal combustion has been observed in internal combustion engines boosted at low speeds and medium to high loads. For example, low-speed pre-ignition (LSPI) may occur randomly and probabilistically during engine operation at speeds below 3000 rpm, under load, and with a mean effective brake pressure (BMEP) of 10 bar or more. The compression stroke time is longest during low-speed engine operation.

[0005] Previous studies have shown that the use of turbochargers, engine design, engine coating, piston shape, fuel selection, and / or engine oil additives may contribute to an increase in LSPI events. Therefore, there is a need for fuel and engine oil additive components and / or combinations that are effective in reducing or eliminating LSPI. SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEM

[0006] overview In one aspect, a fuel composition is provided that includes (1) a hydrocarbon fuel boiling in the gasoline or diesel range and having more than 50% by weight boiling in that range, and (2) a small amount of one or more primary low speed pre-ignition (LSPI) reduction additives including: (i) an amino additive, (ii) an amine additive, (iii) a triazole additive, (iv) a benzamidinium additive, (v) a benzoxazole additive, or (vi) an N═C—X motif additive having the following structure

Chemical formula

[0007] In another aspect, a fuel concentrate is provided that includes (1) an organic solvent boiling in the range of 65° C. to 205° C. and having from 90 to 30% by weight boiling in that range, and (2) from 10 to 70% by weight of an additive component selected from one or more of the following: (i) an amino additive, (ii) an amine additive, (iii) a triazole additive, (iv) a benzamidinium additive, (v) a benzoxazole additive, or (vi) an N═C—X motif additive having the following structure

Chemical formula

[0008] In a further aspect, a lubricating oil composition is provided that includes (1) a base oil in an amount greater than 50% by weight, and (2) from 0.01% to 15% by weight of a component selected from one or more primary low-speed pre-ignition (LSPI) reduction additives, including: (i) an amino additive, (ii) an amine additive, (iii) a triazole additive, (iv) a benzamidinium additive, (v) a benzoxazole additive, or (vi) an N=C-X motif additive having the following structure

Chemical formula

Chemical formula

[10] The fuel composition according to [9], wherein a primary LSPI reduction additive and a secondary LSPI reduction additive form a salt.

[11] The fuel composition according to [9], wherein the acid additive is a fatty acid, an unsaturated acid, an alkyl aromatic acid, an aromatic acid, a hydroxy acid, or an amino acid.

[12] The fuel composition according to [9], wherein the secondary LSPI reducing additive is 2-ethylhexanoate, isostearate, proline, diketone, oleate, toluene, tetraline carboxylate, phenoxide, phenol carboxylate, hydroxy acid, 2-hydroxy-5-(tetracosa-1,3,5,7,9,11,13,15,17,19,21,23-dodecain-1-yl) dihydrogen benzoate or ketoester.

[13] (1) 90-30 wt% organic solvent that boils in the range of 65°C to 205°C, and (2) 10-70 wt% additive component selected from one or more of the following: Fuel concentrates containing: (i) amino additives, (ii) amine additives, (iii) triazole additives, (iv) benzamidinium additives, (v) benzoxazole additives, or (vi) N=CX motif additives having the following structure

change

[14] The fuel concentrate according to

[13] , wherein the amino additive is a beta-aminoalkanol, an amino acid, or an amino ester.

[15] The fuel concentrate according to

[13] , wherein the amine additive is an aromatic amine or an aliphatic amine.

[16] The fuel concentrate according to

[13] , wherein the triazole additive is 5,6-dimethylbenzotriazole.

[17] The fuel concentrate according to

[13] , wherein the primary LSPI reduction additive is prolinol, aliquot, morph gum, 2-aminobenzimidazole, AHPD, N,N-dimethyl-N-octylbenzamidinium-2-oxide, benzoxazole, 2-methylquinoline-8-amine, or 2-aminobenzoxazole.

[18] The fuel concentrate according to

[13] , wherein the N=CX motif additive is amidine, guanidine, imidazole, benzamidine, benzimidazole, or aminobenzimidazole.

[19] The fuel concentrate according to

[18] , wherein the amidine is 1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 2-phenyl-1H-benzo[d]imidazole, or 1,8-diazabicyclo[5.4.0]-undecé-7-ene (DBU).

[20] The fuel concentrate according to

[18] , wherein the guanidine is 1,1,3,3-tetramethylguanidine (TMG), 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), 1,5,7-triazabicyclo[4.4.0]decé-5-ene (TBD), 1,2-diphenylguanidine, or 7-methyl-1,5,7-triazabicyclo[4.4.0]decé-5-ene (MTBD).

[21] The fuel concentrate according to

[13] further comprises a secondary LSPI reducing additive including an acid additive, a phenol additive, a 1,3-dicarbonyl additive, a hydroxamide additive, an antioxidant additive, or a salicylate additive.

[22] The fuel concentrate according to

[21] , wherein the acid additive is a fatty acid, an unsaturated acid, an alkyl aromatic acid, an aromatic acid, a hydroxy acid, or an amino acid.

[23] The fuel concentrate according to

[21] , wherein the secondary LSPI reducing additive is 2-ethylhexanoate, isostearate, proline, diketone, oleate, toluene, tetraline carboxylate, phenoxide, phenol carboxylate, hydroxy acid, or ketoester.

[24] (1) A lubricating oil composition comprising more than 50% by weight of a base oil, and (2) 0.01 to 15% by weight of one or more of the following components: Primary low-speed pre-ignition (LSPI) reduction additives comprising (i) amino additives, (ii) amine additives, (iii) triazole additives, (iv) benzamidinium additives, (v) benzoxazole additives, or (vi) N=CX motif additives having the following structure.

change

[25] The lubricating oil composition according to

[24] , wherein the amino additive is a beta-aminoalkanol, an amino acid, or an amino ester.

[26] The lubricating oil composition according to

[24] , wherein the amine additive is an aromatic amine or an aliphatic amine.

[27] The lubricating oil composition according to

[24] , wherein the triazole additive is 5,6-dimethylbenzotriazole.

[28] The lubricating oil composition according to

[24] , wherein the primary LSPI reducing additive is prolinol, aliquot, morph gum, 2-aminobenzimidazole, AHPD, N,N-dimethyl-N-octylbenzamidinium-2-oxide, benzoxazole, 2-methylquinoline-8-amine, or 2-aminobenzoxazole.

[29] The lubricating oil composition according to

[24] , wherein the N=CX motif additive is amidine, guanidine, imidazole, benzamidine, benzimidazole, or aminobenzimidazole.

[30] The lubricating oil composition according to

[29] , wherein the amidine is 1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 2-phenyl-1H-benzo[d]imidazole, or 1,8-diazabicyclo[5.4.0]-undecé-7-ene (DBU).

[31] The lubricating oil composition according to

[29] , wherein the guanidine is 1,1,3,3-tetramethylguanidine (TMG), 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), 1,5,7-triazabicyclo[4.4.0]decé-5-ene (TBD), 1,2-diphenylguanidine, or 7-methyl-1,5,7-triazabicyclo[4.4.0]decé-5-ene (MTBD).

[32] The lubricating oil composition according to

[24] further comprises a secondary LSPI reducing additive including an acid additive, a phenol additive, a 1,3-dicarbonyl additive, a hydroxamide additive, an antioxidant additive, or a salicylate additive.

[33] The lubricating oil composition according to

[32] , wherein the secondary LSPI reducing additive is 2-ethylhexanoate, isostearate, proline, diketone, oleate, toluene, tetraline carboxylate, phenoxide, phenol carboxylate, hydroxy acid, or ketoester.

[34] A method for preventing or reducing low-speed pre-ignition events in a spark-ignition internal combustion engine, comprising supplying a lubricating oil composition

[24] to the engine.

[35] The method according to

[34] , wherein a spark-ignition internal combustion engine operates at a speed of less than 3000 rpm.

[36] The method according to

[34] , wherein a spark-ignition internal combustion engine is operated under a load having a mean effective brake pressure of at least 10 bar (1 MPa).

[37] A method for preventing or reducing low-speed pre-ignition events in a spark-ignition internal combustion engine, comprising supplying the fuel composition described in [1] to the engine.

[38] The method according to

[37] , wherein a spark-ignition internal combustion engine operates at a speed of less than 3000 rpm.

[39] The method according to

[37] , wherein a spark-ignition internal combustion engine is operated under a load having a mean effective brake pressure of at least 10 bar (1 MPa).

BEST MODE FOR CARRYING OUT THE INVENTION

[0009] Detailed explanation Introduction As used herein, the following words and expressions have the meanings ascribed hereinafter when used and as used.

[0010] "Gasoline" or "gasoline boiling range components" refers to a composition containing at least predominantly C4-C 12 hydrocarbons. In one embodiment, gasoline or gasoline boiling range components refer to a composition containing at least predominantly C4-C 12 hydrocarbons and further having a boiling range from about 100°F (37.8°C) to about 400°F (204°C). In an alternative embodiment, gasoline or gasoline boiling range components are defined to refer to a composition having a boiling range from about 100°F (37.8°C) to about 400°F (204°C) and containing at least predominantly C4-C 12 hydrocarbons and further defined to meet ASTM D4814.

[0011] The term "diesel" refers to at least predominantly C 10 ~C 25This refers to middle distillate fuels containing hydrocarbons. In one embodiment, diesel is at least primarily C 10 ~C 25 It is further defined to refer to a composition containing hydrocarbons and having a boiling point range of about 165.6°C (330°F) to about 371.1°C (700°F). In an alternative embodiment, diesel is at least primarily C 10 ~C 25 It is defined as containing hydrocarbons, having a boiling point range of approximately 165.6°C (330°F) to approximately 371.1°C (700°F), and also satisfying ASTMD975.

[0012] The term "oil-soluble" means that, for a given additive, the amount necessary to provide the desired level of activity or performance can be incorporated by dissolving, dispersing, or suspending it in an oil of lubricating viscosity. Typically, this means that at least 0.001% by weight of the additive can be incorporated into the lubricating oil composition. The term "fuel-soluble" is a similar expression for an additive dissolved, dispersed, or suspended in a fuel.

[0013] The term "alkyl" refers to a saturated hydrocarbon group, which can be linear, branched, cyclic, or a combination of cyclic, linear, and / or branched.

[0014] "Alkanol" is an alkyl group having a hydroxy substituent (i.e., an -OH group), as described herein.

[0015] "Small amount" means less than 50% by weight of the composition, expressed with respect to the listed additives and the total weight of the composition considered to be the active ingredient of the additives.

[0016] An "analog" is a compound that is similar to another compound but has a different structure with respect to one or more specific components, such as atoms, groups, or substructures, which are replaced by other atoms, groups, or substructures.

[0017] A "congener" is a compound belonging to a series of compounds in which the repeating units differ from one another. Alkanes are an example of congeners. For example, ethane and propane are congeners because they differ only in the length of their repeating units (-CH2-). Congeners can be considered analogous to certain types of compounds.

[0018] A "derivative" is a compound derived from a similar compound through a chemical reaction (e.g., acid-base reaction, hydrogenation, etc.). In the context of substituents, a derivative can be a combination of one or more moieties. For example, a phenol moiety can be considered a derivative of an aryl moiety and a hydroxyl moiety. Those skilled in the art will know the boundaries of what is considered a derivative. The term "substituted" refers to the substitution or exchange of one or more atoms in a compound. As an exemplary example, a "substituted alkyl group" may refer, among other things, to ethanol.

[0019] An "engine" or "combustion engine" is a heat engine in which the combustion of fuel occurs within a combustion chamber. An "internal combustion engine" is a heat engine in which the combustion of fuel occurs within a confined space ("combustion chamber"). A "spark-ignition engine" is a heat engine in which combustion is ignited, usually by a spark from a spark plug. This is in contrast to a "compression-ignition engine," usually a diesel engine. In this engine, the heat generated by compression and fuel injection is sufficient to start combustion without an external spark.

[0020] Low-speed pre-ignition (LSPI) Low-speed pre-ignition (LSPI) is most likely to occur in direct-injection, boost (turbocharger or supercharger), and spark-ignition (gasoline) internal combustion engines, generating a mean effective brake pressure level exceeding 1000 kPa (10 bar) during operation at engine speeds of 1500-2500 revolutions per minute (rpm), such as 1500-2000 rpm. Mean effective brake pressure (BMEP) is defined as the work achieved during an engine cycle divided by the engine sweep volume, with engine torque normalized by engine displacement. The term "brake" refers to the actual torque or power available at the engine flywheel, as measured by a dynamometer. Therefore, BMEP is a measure of the engine's effective energy output.

[0021] The fuel composition or lubricating oil composition of this disclosure is particularly useful in high-pressure spark-ignition internal combustion engines and has been found to minimize or prevent engine knocking and pre-ignition problems when used in such engines.

[0022] Primary LSPI reduction additive The following describes primary additives that can be used as fuel or lubricant additives to reduce LSPI activity. Primary LSPI reducing additives can be used alone, and / or in combination with other primary additives, and / or in combination with one or more secondary LSPI reducing additives (described below). When multiple additives are used, the additives may be in the form of salts. Furthermore, when two or more additives are used, there may be synergistic effects between the two or more additives. In general, these additives are soluble in fuel or oil at the concentration necessary to achieve the desired LSPI reduction level. Table 1 summarizes the types of primary additives. [Table 1]

[0023] 1. Amino additives β-aminoalkanol The fuel additives or lubricant additives of this disclosure may be β-aminoalkanols, substituted β-aminoalkanols, derivatives thereof, or acceptable salts thereof. Useful β-aminoalkanols include those that can be represented by the following general formula: [ka] Here, R1, R2, R3, and R4 are hydrogen and C1-C, respectively. 20 The alkyl groups (e.g., C1-C6 alkyl groups) are independently selected. Two or more R1, R2, R3, and R4 may optionally bond together to form a ring structure (e.g., a 5-membered, 6-membered, or 7-membered ring). In some embodiments, R1, R2, R3, and R4 may independently comprise one or more aromatic rings.

[0024] β-aminoalkanols have at least two carbon atoms (for example, 4 to 30 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 16 carbon atoms, or 5 to 12 carbon atoms).

[0025] Representative examples of suitable β-aminoalkanols include: ethanolamine (Formula 1A), 1-amino-2-propanol (Formula 1B), alaninol (Formula 1C), 2-(methylamino)ethanol (Formula 1D), 2-(ethylamino)ethanol (Formula 1E), 2-amino-2-methyl-1-propanol (Formula 1F), 2-amino-1-butanol (Formula 1G), 2-amino-1-pentanol (Formula 1H), valinol (Formula 1I), 2-amino-1-hexanol (Formula 1J), leucinol (Formula 1K), isoleucinol (Formula 1L), cycloleucinol (Formula 1M), cyclohexylglycinol (Formula 1N), prolinol (Formula 1O), 2-(hydroxymethyl)piperidine (Formula 1P), 2-aminocyclopentanol (Formula 1Q), and 2-aminocyclohexanol (Formula 1R). Typical structures are shown below. [ka] [ka]

[0026] amino acid The fuel additives or lubricant additives of this disclosure may be aliphatic amino acids, substituted aliphatic amino acids, derivatives thereof, or acceptable salts thereof. Useful amino acids include those that can be represented by the following general formula: [ka] Here, R is either an "aliphatic" or "aromatic" side chain. Amino acid side chains can be broadly classified into aromatic or aliphatic. Aromatic side chains contain an aromatic ring. Examples of amino acids with aromatic side chains include histidine (formula 2A), phenylalanine (formula 2B), tyrosine (formula 2C), and tryptophan (formula 2D). Non-aromatic side chains are broadly classified as "aliphatic" and include, for example, alanine (formula 2E), glycine (formula 2F), and cysteine ​​(formula 2G).

[0027] Amino acids can be natural and / or non-natural α-amino acids. Natural amino acids are those encoded by the genetic code and those derived therefrom. These include, for example, hydroxyproline (formula 2H), γ-carboxyglutamate (formula 2I), and citrulline (formula 2J). In this specification, the term “amino acid” also includes amino acid analogs and mimics. Analogs are compounds that have the same general structure as natural amino acids, except that the R group is not found in natural amino acids.

[0028] Representative examples of naturally occurring amino acid analogs include homoserine (formula 2K), norleucine (formula 2L), homoproline (formula 2M), and proline (formula 2N). Amino acid mimes are compounds that have a different chemical structure from the typical α-amino acid but function similarly. Amino acids can be L- or D-amino acids. Representative structures are shown below. [ka] [ka]

[0029] Amino esters The fuel additives or lubricant additives of this disclosure may be amino esters, substituted amino esters, derivatives thereof, or acceptable salts thereof. Amino esters can be derived from amino acids (as described above) and alcohols. Amino esters and amino acids can be considered derivatives of each other. Useful amino esters include those that can be represented by the following general formula: [ka] Here, R is an aliphatic side chain, and R1 is a carbon chain with a length of 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms, particularly methanol or ethanol, preferably methanol.

[0030] Amino esters may contain aromatic or aliphatic side chains. Representative examples of amino esters include methyl alaninate (formula 3A), ethyl alaninate (formula 3B), methyl glycinate (formula 3C), and ethyl glycinate (formula 3D). Representative structures are shown below. [ka]

[0031] 2. N=CX motif additive The fuel additive or lubricating oil additive of this disclosure may have an N=CX motif as shown in the following generalized structure. [ka] Here, R is H, a monovalent organic group, or a monovalent heteroorganic group (described in more detail below), X1 and X2 are independently H, C, N, O, or S, and X1 or X2 is independently one or more C1-C 20 It comprises an alkyl group (e.g., C1-C6 alkyl) or one or more aromatic rings. In some embodiments, X1 and X2 may comprise a cyclic structure (e.g., a 5-membered, 6-membered, or 7-membered ring). The cyclic structure may be aromatic or non-aromatic and may vary from fully saturated to fully unsaturated. Suitable examples of additives compatible with Formula 4 include amidine, guanidine, imidazole, benzamidine, benzimidazole, and aminobenzimidazole.

[0032] Amidine The fuel additives or lubricating oil additives of this disclosure may be amidines, substituted amidines, derivatives thereof, or acceptable salts thereof. Useful amidines include those that can be represented by the following general formula: [ka] Here, R5, R6, R7, and R8 are independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., nitrogen, oxygen, sulfur, or phosphorus in the form of a group or part that is bonded via a carbon atom but does not contain an acidic functional group such as a carboxylic acid or sulfonic acid), and combinations thereof. Any two or more of R5, R6, R7, and R8 may optionally bond together to form a cyclic structure (e.g., a 5-membered, 6-membered, or 7-membered ring). The cyclic structure can be aromatic or aromatic, and can vary from fully saturated to fully unsaturated. The organic and heteroorganic groups may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms).

[0033] Representative examples of suitable amidines include 1,4,5,6-tetrahydropyrimidine (Formula 5A), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (Formula 5B), 1,2-diethyl-1,4,5,6-tetrahydropyrimidine (Formula 5C), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN; Formula 5D), 1,8-diazabicyclo[5.4.0]-undeca-7-ene (DBU; Formula 5E), benzamidine (Formula 5F), benzimidazole (Formula 5G), and 2-phenyl-1H-benzo[d]imidazole (Formula 5M). Representative structures are shown below. [ka]

[0034] Guanidine The fuel additives or lubricant additives of this disclosure may be guanidine, substituted guanidine, or derivatives thereof, or acceptable salts thereof. Useful guanidines include those that can be represented by the following general formula: [ka] Here, R9, R 10 , R 11 , R 12 and R 13Each is independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (for example, nitrogen, oxygen, sulfur, or phosphorus in the form of a group or part that is bonded via a carbon atom but does not contain an acidic functional group such as a carboxylic acid or sulfonic acid) and combinations thereof. Then R9, R 10 , R 11 , R 12 and R 13 Any two or more of these can, if applicable, bond together to form a cyclic structure (e.g., a five-membered, six-membered, or seven-membered ring). The cyclic structure can be aromatic or aromatic, and can vary from fully saturated to fully unsaturated. Organic and heteroorganic groups can have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms).

[0035] Representative examples of suitable guanidines include 1,1,3,3-tetramethylguanidine (TMG; Formula 6A), 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG; Formula 6B), 1,5,7-triazabicyclo[4.4.0]decé-5-ene (TBD; Formula 6C), 7-methyl-1,5,7-triazabicyclo[4.4.0]decé-5-ene (MTBD; Formula 6D), and 1,2-diphenylguanidine (Formula 6I). Representative structures are shown below. [ka] [ka]

[0036] Imidazole The fuel additives or lubricating oil additives of this disclosure may be imidazoles, substituted imidazoles, derivatives thereof, or acceptable salts thereof. Suitable imidazoles include imidazole (formula 7A), 1-methylimidazole (formula 7B), 1-ethylimidazole (formula 7D), 1-propylimidazole (formula 7E), 1-n-butylimidazole (formula 7F), 1-decylimidazole, 1-dodecylimidazole, 2-methylimidazole (formula 7G), 2-ethylimidazole, 2-isopropylimidazole (formula 7H), 4-methylimidazole (formula 7I), 1,2-dimethylimidazole (formula 7J), 2-ethyl-4(5)-methylimidazole (formula 7K), and 1-vinylimidazole (formula 7L). Representative structures are shown below. [ka]

[0037] 3. Triazole additive The fuel additives or lubricant additives of this disclosure may be triazoles, substituted triazoles, derivatives thereof, or acceptable salts thereof. Suitable triazoles include 1,2,3-triazole (formula 8A), 5,6-dimethylbenzotriazole (formula 8B), and 1,2,4-triazole (formula 8C). Representative structures are shown below. [ka] [ka]

[0038] 4. Benzamidinium additive The fuel additives or lubricating oil additives of this disclosure may be benzamidinium, substituted benzamidinium, or derivatives thereof, or acceptable salts thereof. Useful benzamidinium additives include those that can be represented by the following general formula 9, where R1, R2, and R3 are independently C1-C 20 It is an alkyl group. [ka]

[0039] Suitable benzamidinium compounds include N,N-dimethyl-N-octylbenzamidium-2-oxide (formula 9A). A typical structure is shown below. [ka] [ka]

[0040] 5. Benzoxazole additive The fuel additives or lubricant additives of this disclosure may be benzoxazoles, substituted benzoxazoles, derivatives thereof, or acceptable salts thereof. Suitable benzoxazoles include benzoxazole (formula 10A) and 2-aminobenzoxazole (formula 10B). Representative structures are shown below. [ka]

[0041] 6. Amine additives Aromatic amines The fuel additives or lubricating oil additives of this disclosure may be aromatic amines, substituted aromatic amines, derivatives thereof, or acceptable salts thereof. Aromatic amine additives may have the generalized structures shown in formulas 11-1 or 11-2. [ka] Here, R is independently one or more H or C1-C 20 It is an alkyl group, and X is N (e.g., RNR) or O.

[0042] Suitable aromatic amines include 2-methylquinoline-8-amine (formula 11A). A typical structure is shown below. [ka]

[0043] Aliphatic amines Suitable aliphatic amines are listed below. [ka]

[0044] Secondary LSPI reduction additive The following describes secondary LSPI reducing additives that can be used as fuel or lubricant additives to reduce LSPI activity. Generally, secondary LSPI reducing additives, substituted secondary LSPI reducing additives, or their derivatives are used in combination with primary additives in the form of their salts to reduce LSPI activity. For example, a combination of β-aminoalkanol (primary additive) and aliphatic acid (secondary additive) can be used as an LSPI additive. Table 2 shows the types of secondary additives. Some additives can function as both primary and / or secondary additives. [Table 2]

[0045] 7. Acid additives aliphatic acid Aliphatic acids are non-aromatic carboxylic acids. Suitable fatty acids include monocarboxylic acids having the following structures: [ka] Here, R is an aliphatic group having 2 to 20 carbon atoms. The aliphatic group can be linear or branched and may contain heteroatoms.

[0046] Appropriate fatty acids include the following: hexanoic acid (formula 13A), heptanoic acid (formula 13B), octanoic acid (formula 13C), nonanoic acid (formula 13D), decanoic acid (formula 13E), undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid (C 20 ), behenic acid (C 22 ), 2-ethylbutyric acid (formula 13F), 3,3-dimethylbutyric acid, 2-methylpentanoic acid (C6), 2-methylhexanoic acid (C7), 4-methylhexanoic acid (C7), 5-methylhexanoic acid (C7), 2,2-dimethylpentanoic acid (C7), 2-propylpentanoic acid (C8), 2-ethylhexanoic acid (formula 13G), 2-methylheptanoic acid (C8), isooctanoic acid (C8), 3,5,5-trimethylhexanoic acid (C9), 4-methyloctanoic acid (C9), 4-methylnonanoic acid, (C 10 ), isodecanoic acid (C 10 ), 2-butyloctanoic acid (C 12 ), isotridecanoic acid (C 13 ), 2-hexyldecanoic acid (C 16 ), isopalmitic acid (C 16 ), isostearic acid (formula 13H), 3-cyclohexylpropionic acid, 4-cyclohexylbutyric acid (formula 13I), and cyclohexopentanoic acid. Representative structures are shown below. [ka] [ka]

[0047] unsaturated acid Suitable unsaturated acids include any organic acid containing double or triple carbon-carbon bonds. Representative unsaturated acids include maleic acid (formula 14A), fumaric acid (formula 14B), and unsaturated fatty acids such as palmitoleic acid (formula 14C) and oleic acid (formula 14D). Representative structures are shown below. [ka]

[0048] Alkyl aromatic acids Suitable alkyl aromatic acids include both monocarboxylic acids and dicarboxylic acids. Alkyl carboxylic acids may have six or more carbon atoms (e.g., 6-24 carbon atoms, 6-20 carbon atoms, 8-24 carbon atoms, 8-20 carbon atoms, or 8-18 carbon atoms). The alkyl moiety may optionally be substituted with one or more substituents such as hydroxyl, alkoxy, and carbonyl (e.g., aldehyde or ketone) groups. Suitable examples of alkyl aromatic acids include methylbenzoic acid (formula 15A) and ethylbenzoic acid (formula 15B). Representative structures are shown below. [ka]

[0049] aromatic acid Suitable aromatic acids include both monocarboxylic acids and dicarboxylic acids. Alkylcarboxylic acids may have six or more carbon atoms (e.g., 6-24 carbon atoms, 6-20 carbon atoms, 8-24 carbon atoms, 8-20 carbon atoms, or 8-18 carbon atoms). The alkyl moiety may optionally be substituted with one or more substituents such as hydroxy, alkoxy, and carbonyl (e.g., aldehyde or ketone) groups. Suitable aromatic acids include benzoic acid (formula 16A), hydroxybenzoic acid (formula 16B), and tetralinecarboxylic acid (formula 16C). Representative structures are shown below. [ka]

[0050] Hydroxy acid Suitable hydroxy acids include those that can be represented by the following general formula. [ka] Here, n=1 to 3. Suitable examples of hydroxy acids include glycolic acid (formula 17A), lactic acid (formula 17B), malic acid (formula 17C), tartaric acid (formula 17D), and citric acid (formula 17E). Representative structures are shown below. [ka] [ka]

[0051] amino acid Amino acids can be used as primary and / or secondary additives. Suitable amino acids were previously listed above.

[0052] 8. Phenolic additives phenol Suitable phenols include thymol (formula 18A), eugenol (formula 18B), hydroquinone (formula 18C), resorcinol (formula 18D), cresol (formula 18E), and 2-methylquinoline-8-ol (formula 18G). Representative structures are shown below. [ka]

[0053] 9.1,3 Dicarbonyl Additives 1,3-diketones Suitable examples of 1,3-diketone compounds include acetylacetone (formula 19A) and curcumin (formula 19B). Representative structures are shown below. [ka]

[0054] 1,3-ketoesters The following are suitable 1,3-ketoesters. [ka]

[0055] 10. Hydroxamidic acid additive Hydroxamides are hydroxy derivatives of amides. Useful hydroxamides include those that can be represented by the following general formula. [ka] Here, R1 and R2 are hydrogen or C1-C, respectively. 20 (For example, C3-C 12 ) is selected independently of alkyl groups. Suitable hydroxamides include hydroxymethylacetamide (formula 21A). A typical structure is shown below. [ka]

[0056] 11. Antioxidant Additives Suitable antioxidants include both monocarboxylic acids and dicarboxylic acids. Alkylcarboxylic acids may have six or more carbon atoms (e.g., 6-24 carbon atoms, 6-20 carbon atoms, 8-24 carbon atoms, 8-20 carbon atoms, or 8-18 carbon atoms). The alkyl moiety may optionally be substituted with one or more substituents such as hydroxyl, alkoxy, and carbonyl (e.g., aldehyde or ketone) groups. Suitable antioxidants include: [ka]

[0057] 12. Salicylate additives Salicylate Suitable salicylates include 2-hydroxy-5-(tetracosa-1,3,5,7,9,11,13,15,17,19,21,23-dodecain-1-yl)dihydrogen benzoate (formula 23E). Suitable salicylates are listed below. [ka]

[0058] salt The salts of this disclosure can be prepared by conventional means, for example, by mixing a primary additive with a suitable secondary additive in an aprotic solvent. The order in which one additive is added to the other is not important. The primary and secondary additives are usually mixed in approximately equimolar ratios. Excess primary or secondary additive components can be used. For example, the molar ratio of the base to the alkylcarboxylic acid can be about 1.05:1 to 2:1 (e.g., 1.1:1 to 1.5:1). Representative salts are shown below. [ka] [ka] [ka] [ka] [ka] [ka]

[0059] fuel composition The compounds of this disclosure may be useful as additives in hydrocarbon fuels for preventing or reducing engine knocking or pre-ignition events in spark-ignition internal combustion engines.

[0060] The concentration of the compounds of this disclosure in hydrocarbon fuels may range from 25 to 5,000 parts per million (ppm) by weight (e.g., 50 to 1,000 ppm).

[0061] The compounds of this disclosure can be formulated as concentrates using inert, stable, lipophilic (i.e., soluble in hydrocarbon fuels) organic solvents that boil in the range of 65°C to 205°C. Aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene, or high-boiling aromatic or aromatic thinners can be used. Aliphatic alcohols containing 2 to 8 carbon atoms, such as ethanol, isopropanol, methyl isobutylcarbinol, and n-butanol, are also suitable for use with the additive in combination with the hydrocarbon solvent. In the concentrate, the amount of the additive may range from 10 to 70% by weight (e.g., 20 to 40% by weight).

[0062] In gasoline fuels, other well-known additives can be used, including oxygenated compounds (e.g., ethanol, methyl tert-butyl ether), other anti-knock agents, and cleaning / dispersing agents (e.g., hydrocarbylamines, hydrocarbyl poly(oxyalkylene)amines, succinimide, Mannich reaction products, aromatic esters of polyalkylphenoxyalkanols, or polyalkylphenoxyaminoalkanes). Furthermore, friction modifiers, antioxidants, metal deactivators, and deemulsifiers may be present.

[0063] In diesel fuels, other well-known additives such as pour point depressants, flow improvers, and cetane improvers can be used.

[0064] Fuel-soluble non-volatile carrier fluids or oils may also be used in conjunction with the compounds of this disclosure. The carrier fluid is a chemically inert hydrocarbon-soluble liquid vehicle that substantially increases the non-volatile residue (NVR), or solvent-free liquid fraction of the fuel additive composition, while not overwhelmingly contributing to the increase in octane requirements. The carrier fluid may be natural or synthetic oils such as mineral oil, refined petroleum oil, synthetic polyalkanes and alkenes including hydrogenated and non-hydrogenated polyalphaolefins, and synthetic polyoxyalkylene-derived oils, which are described in U.S. Patent Nos. 3,756,793; 4,191,537; and 5,004,478; and European Patent Applications Nos. 356,726 and 382,159.

[0065] The carrier fluid can be used in amounts ranging from 35 to 5000 ppm by weight of the hydrocarbon fuel (e.g., 50 to 3000 ppm of the fuel). When used in fuel concentrates, the carrier fluid may be present in amounts ranging from 20 to 60% by weight (e.g., 30 to 50% by weight).

[0066] lubricating oil composition The compounds of this disclosure may be useful as additives in lubricating oils to prevent or reduce engine knocking or pre-ignition events in spark-ignition internal combustion engines.

[0067] The concentration of the compound of this disclosure in the lubricating oil composition may range from 0.01 to 15% by weight (e.g., 0.5 to 5% by weight) based on the total weight of the lubricating oil composition.

[0068] Lubricating viscosity oils (sometimes called "base stock" or "base oil") are the primary liquid component of a lubricant, and are blended with additives and, if necessary, other oils to produce, for example, a final lubricant (or lubricant composition). Base oils useful for producing concentrates and from which lubricating oil compositions can be selected from natural (plant, animal, or mineral) and synthetic lubricants and mixtures thereof.

[0069] The definitions of base stock and base oil in this disclosure are the same as those found in American Petroleum Institute (API) Publication 1509 Annex E ("API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils," December 2016). Group I base stocks contain less than 90% saturated material and / or more than 0.03% sulfur, and have a viscosity index of 80 or greater and less than 120, using the test methods specified in Table E-1. Group II base stocks contain 90% or more saturated material and 0.03% or less sulfur, and have a viscosity index of 80 or greater and less than 120, using the test methods specified in Table E-1. Group III base stocks contain 90% or more saturated material and 0.03% or less sulfur, and have a viscosity index of 120 or greater, using the test methods specified in Table E-1. Group IV base stocks are polyalphaolefins (PAOs). Group V base stocks include all other base stocks not included in Groups I, II, III, or IV.

[0070] Natural oils include animal oils, vegetable oils (e.g., castor oil and lard), and mineral oils. Animal and vegetable oils with good thermal oxidative stability can be used. Among natural oils, mineral oil is preferred. Mineral oils vary considerably in terms of their source of crude oil, such as whether they are paraffinic, naphthenic, or paraffinic-naphthenic mixtures. Oils derived from coal and shale are also useful. Natural oils also vary depending on the methods used in their production and refining, such as the range of distillation and whether the process is straight-run, cracking, hydrorefining, or solvent extraction.

[0071] Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized and crosspolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymer, ethylene-olefin copolymer, and ethylene-alphaolefin copolymer). Polyalphaolefin (PAO) oil-based stocks are commonly used synthetic hydrocarbon oils. For example, C8 to C 14 Olefins, for example, C8, C 10 , C 12 , C 14 PAO derived from olefins or mixtures thereof can be used.

[0072] Other useful fluids for use as base oils include, preferably, catalytically treated or synthesized unconventional or unconventional base stocks to provide high-performance properties.

[0073] Non-conventional or unconventional base stocks / base oils include one or more mixtures of base stocks derived from one or more gas-to-liquid (GTL) materials, as well as mineral and / or non-mineral waxy raw materials such as isomerate / iso-dewaxed base stocks derived from natural waxes or waxy feeds, slack wax, natural waxes, and non-petroleum-derived waxy materials such as waxy stocks derived from gas oil, waxy fuel hydrocracking unit bottoms, waxy raffinates, hydrocracking products, pyrocracking products, or other mineral oils, or waxy substances received from liquefied coal or shale oil, and mixtures of such base stocks.

[0074] The base oils used in the lubricating oil compositions of this disclosure are API Group I, Group II, Group III, Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof, more preferably any of the various oils corresponding to Group III to Group V base oils due to their exceptional volatility, stability, viscosity, and cleanliness characteristics.

[0075] Typically, base oils have a kinematic viscosity of 2.5 to 20 mmHg at 100°C. 2 / second (for example, 3 to 12mm) 2 / second, 4 to 10mm 2 / second, or 4.5 to 8mm 2 It is within the range of / s).

[0076] The lubricating oil compositions of this invention may also include conventional lubricating oil additives to impart auxiliary functions and give a finished lubricating oil composition in which these additives are dispersed or dissolved. For example, the lubricating oil compositions may be blended with antioxidants, ashless dispersants, anti-wear agents, cleaning agents such as metal cleaners, rust inhibitors, anti-fogging agents, demulsifiers, friction modifiers, metal deactivators, injection point depressants, viscosity modifiers, defoaming agents, cosolvents, package compatibilizers, corrosion inhibitors, dyes, extreme pressure agents, and mixtures thereof. A variety of additives are known and commercially available. These additives, or compounds similar thereto, can be used in the preparation of the lubricating oil compositions of this invention by conventional mixing procedures.

[0077] Each of the aforementioned additives, when used, is used in a functionally effective amount to impart the desired properties to the lubricant. Therefore, for example, if the additive is an ashless dispersant, a functionally effective amount of this ashless dispersant would be sufficient to impart the desired dispersion properties to the lubricant. Generally, the concentration of each of these additives, when used, can range from about 0.001 to about 20% by weight, for example, from about 0.01 to about 10% by weight, unless otherwise specified.

[0078] example The following examples are intended to be non-restrictive.

[0079] Example 1-45 The test compounds were mixed in gasoline or lubricating oil, and their ability to reduce LSPI events was determined using the test methods described below.

[0080] A GM 2.0L LHU four-cylinder gasoline turbocharged direct-injection engine was used in the LSPI test. Each cylinder was equipped with a combustion pressure sensor.

[0081] A 6-segment test procedure was used to determine the number of LSPI events occurring under engine speed of 2000 rpm and load of 275 Nm. The LSPI test conditions were run for 28 minutes, with each segment separated by an idle period. The first segment was used for oil conditioning, and the number of LSPI events was not counted. Each segment was slightly truncated to eliminate transient portions. Each truncated segment typically has approximately 100,000 combustion cycles (25,000 combustion cycles per cylinder). In total, the five truncated segments from which LSPI events are counted have approximately 500,000 combustion cycles (125,000 combustion cycles per cylinder). If the engine cannot complete all six segments, the test may be shortened.

[0082] LSPI-affected combustion cycles were determined by monitoring peak cylinder pressure (PP) and crank angle at 5% total heat release (AI5). An LSPI-affected combustion cycle is defined as having both (1) a PP greater than 5 standard deviations above the average PP for a particular cylinder and truncated segment, and (2) an AI5 greater than 5 standard deviations above the average for a particular cylinder and truncated segment.

[0083] The LSPI frequency is reported as the number of LSPI-affected combustion cycles per million combustion cycles and is calculated as follows: LSPI frequency = [(Total number of combustion cycles affected by LSPI in the 5 truncated segments) / (Total number of combustion cycles in the 5 truncated segments)] × 1,000,000

[0084] Additives associated with a test fuel and / or test lubricant that reduce LSPI frequency compared to the corresponding baseline fuel and / or baseline lubricant are considered LSPI-reducing additives. In the tests here, the baseline fuel was conventional 49-state premium unleaded gasoline fuel without deposit control additives, and the baseline lubricant was representative of conventional engine oil meeting ILSAC GF-5 and API SN specifications. In some tests, tetralin was added to the gasoline to promote LSPI. The test results are shown in Table 2. [Table 2-1] [Table 2-2] [Table 2-3]

Claims

1. (1) If the amount of hydrocarbon fuel that boils within the gasoline range exceeds 50 wt%, (2) Contains a small amount of primary low-speed pre-ignition (LSPI) reduction additive: (3) Contains a small amount of secondary LSPI reducing additives including acid additives, phenol additives, 1,3-dicarbonyl additives, hydroxamide additives, antioxidant additives, or salicylate additives. The primary LSPI reducing additive is prolinol. A fuel composition, Furthermore, the fuel composition wherein the primary LSPI reducing additive and the secondary LSPI reducing additive form a salt.

2. The fuel composition according to claim 1, wherein the secondary LSPI reducing additive is 2-ethylhexanoate, isostearate, proline, diketone, oleate, tetraline carboxylate, phenoxide, phenol carboxylate, hydroxy acid, 2-hydroxy-5-(tetracosa-1,3,5,7,9,11,13,15,17,19,21,23-dodecain-1-yl) dihydrogen benzoate or ketoester.

3. (1) 90 to 30 wt% organic solvent that boils in the range of 65°C to 205°C, (2) 10 to 70 wt% of primary LSPI reducing additive components, (3) A small amount of secondary LSPI reducing additive containing an acid additive, phenol additive, 1,3-dicarbonyl additive, hydroxamide additive, antioxidant additive, or salicylate additive, Including, The primary LSPI reducing additive is prolinol. Fuel concentrate, Furthermore, the fuel concentrate wherein the primary LSPI reducing additive and the secondary LSPI reducing additive form salts.

4. The fuel concentrate according to claim 3, wherein the secondary LSPI reducing additive is 2-ethylhexanoate, isostearate, proline, diketone, oleate, tetraline carboxylate, phenoxide, phenol carboxylate, hydroxy acid, or ketoester.

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