Composition for mitigating low speed pre-ignition events

Abstract

Fuel compositions for preventing or reducing low speed pre-ignition events in a spark-ignition internal combustion engine are provided. The fuel compositions include a hydrocarbon fuel having a boiling point in the gasoline or diesel range and a primary additive having a structure given by the formula below or a salt thereof. A is a ring moiety; R1and R2are independently H, C1-C 20 a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group. R3and R4are independently H, C1-C 20 a hydrocarbyl group, a carboxyl group, an ether, an amino, or a hydroxyl group, or where R3and R4are part of a cyclic group. R5is C1-C 100 a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group; and p is 0 to 2, n is 1 to 3, m is 1 to 3, and p+n+m is less than 5.

Description

Technical Field

[0001] This disclosure relates to compositions for preventing or mitigating low-speed pre-ignition events in direct injection engines and methods of using them. Background Technology

[0002] Turbocharged or supercharged engines (i.e., turbocharged internal combustion engines) may exhibit an abnormal combustion phenomenon known as random pre-ignition or low-speed pre-ignition (or "LSPI"). LSPI can lead to high in-cylinder pressure and advanced combustion phase, which can cause severe knocking. In the worst case, LSPI can cause catastrophic engine damage. However, because LSPI events occur only occasionally and in an uncontrolled manner, it is difficult to determine the cause of this phenomenon and develop solutions to suppress it.

[0003] One possible explanation for LSPI is that these events are at least partly caused by the spontaneous combustion of engine oil droplets that enter the engine combustion chamber under high pressure from the piston gap during the period when the engine is running at low speed and the compression stroke is the longest.

[0004] While new engine technologies (such as electronic control and knock sensors) are being actively researched and developed in an attempt to address LSPI, there is also a need for fuel and / or lubricant compositions that can reduce or eliminate LSPI. Summary of the Invention

[0005] In one aspect, a fuel composition is provided, the fuel composition comprising: a hydrocarbon fuel with a boiling point in the range of gasoline or diesel; and a main additive having a structure given by the following formula.

[0006]

[0007] Or its salt; wherein A is a cyclic moiety; wherein R1 and R2 are independently H, Cl-C 20 Hydrocarbon group, carboxyl group, ether or hydroxyl group; wherein R3 and R4 are independently H, C1-C 20 A hydrocarbon group, a carboxyl group, an ether, an amino group, or a hydroxyl group, or wherein R3 and R4 are part of a cyclic group; R5 is C1-C 100 A hydrocarbon group, a carboxyl group, an ether or a hydroxyl group; wherein p is 0 to 2, n is 1 to 3, m is 1 to 3, and p+n+m is less than 5.

[0008] On the other hand, a method is provided for preventing or reducing low-speed pre-ignition events in a spark-ignition internal combustion engine, the method comprising: supplying a fuel composition to the engine, the fuel composition comprising: a hydrocarbon fuel having a boiling point in the range of gasoline or diesel; and a main additive having a structure given by the following formula.

[0009]

[0010] Or its salt; wherein A is a cyclic moiety; wherein R1 and R2 are independently H, Cl-C 20 Hydrocarbon group, carboxyl group, ether or hydroxyl group; wherein R3 and R4 are independently H, C1-C 20 A hydrocarbon group, a carboxyl group, an ether, an amino group, or a hydroxyl group, or wherein R3 and R4 are part of a cyclic group; R5 is C1-C 100 A hydrocarbon group, a carboxyl group, an ether or a hydroxyl group; wherein p is 0 to 2, n is 1 to 3, m is 1 to 3, and p+n+m is less than 5.

[0011] In another aspect, a lubricating oil composition is provided, the lubricating oil composition comprising: a base oil with a lubricating viscosity; and a main additive having a structure given by the following formula.

[0012]

[0013] Or its salt; wherein A is a cyclic moiety; wherein R1 and R2 are independently H, Cl-C 20 Hydrocarbon group, carboxyl group, ether or hydroxyl group; wherein R3 and R4 are independently H, C1-C 20 A hydrocarbon group, a carboxyl group, an ether, an amino group, or a hydroxyl group, or wherein R3 and R4 are part of a cyclic group; R5 is C1-C 100 A hydrocarbon group, a carboxyl group, an ether or a hydroxyl group; wherein p is 0 to 2, n is 1 to 3, m is 1 to 3, and p+n+m is less than 5. Detailed Implementation

[0014] introduction

[0015] In this specification, the following words and expressions, if used and when used, shall have the following meanings.

[0016] "Gasoline" or "gasoline boiling range components" refers to gasoline that primarily contains C4-C4. 12 A composition of hydrocarbons. In one embodiment, gasoline or gasoline boiling range components are further defined as containing at least predominantly C4-C64. 12 The composition further comprises hydrocarbons and has a boiling range of about 100℉ (37.8℃) to about 400℉ (204℃). In an alternative embodiment, gasoline or gasoline boiling range component is defined as referring to a composition that primarily contains C4-C 12 Hydrocarbons, having a boiling range of about 100℉ (37.8°C) to about 400℉ (204°C) and further defined as compositions conforming to ASTM D4814.

[0017] The term "oil-soluble" means that, for a given additive, the amount required to provide the desired level of activity or performance can be incorporated by dissolving, dispersing, or suspending it in an oil having a lubricating viscosity. Typically, this means that at least 0.001% by weight of the additive can be incorporated into a lubricating oil composition. The term "fuel-soluble" is a similar expression for additives that are dissolved, dispersed, or suspended in fuel.

[0018] "A small amount" means less than 50% by weight of the composition, which is expressed in relation to the additive and the total weight of the composition, and is considered to be the active ingredient of the additive.

[0019] An "engine" or "combustion engine" is a thermal engine in which the combustion of fuel occurs in a combustion chamber. An "internal combustion engine" is a thermal engine in which the combustion of fuel occurs in a confined space ("combustion chamber"). A "spark-ignition engine" is a thermal engine in which combustion is ignited by a spark, typically from a spark plug. This contrasts with a "compression-ignition engine" (typically a diesel engine), in which the heat generated by compression along with the injection of fuel is sufficient to ignite combustion without an external spark.

[0020] Low-speed pre-ignition (LSPI)

[0021] Low-speed pre-ignition (LSPI) is most likely or more likely to occur in direct-injection, turbocharged (turbocharged or supercharged), spark-ignition (gasoline) internal combustion engines that produce a mean effective braking pressure level greater than 1000 kPa (10 bar) at engine speeds of 1500 to 2500 rpm (e.g., at engine speeds of 1500 to 2000 rpm). Mean effective braking pressure (BMEP) is defined as the work done during one engine cycle divided by the engine scavenging volume, with engine torque normalized to engine displacement. The term "braking" refers to the actual torque or power available at the engine flywheel, as measured on a dynamometer. Therefore, BMEP is a measure of the engine's useful energy output.

[0022] It has been found that the fuel additives or lubricant additives disclosed herein are particularly useful in high-pressure spark ignition internal combustion engines, and when used in high-pressure spark ignition internal combustion engines, they will prevent or minimize engine knock and pre-ignition problems.

[0023] Phenolamine

[0024] The fuel or lubricant additives of the present invention comprise phenolic amine compositions having the following general formula 1 or salts thereof:

[0025]

[0026] For structure 1, n is 1 to 3, p is 0 to 2, and m is 1 to 3, where p + m + n < 5.

[0027] Part A is a ring, such as an aromatic ring or a heterocyclic ring.

[0028] Each R1 is independently hydrogen, C1-C 20 Hydrocarbon groups, carboxyl groups (e.g., carboxylic acids, esters, amides, ketones, etc.), ethers, or hydroxyl groups.

[0029] Each R2 is independently hydrogen, C1-C 20 Hydrocarbon groups, carboxyl groups (e.g., carboxylic acids, esters, amides, ketones, etc.), ethers, or hydroxyl groups.

[0030] Each R3 is independently hydrogen, C1-C 20 Hydrocarbon groups, carboxyl groups (e.g., carboxylic acids, esters, amides, ketones, etc.), ethers, amino or hydroxyl groups.

[0031] Each R4 is independently hydrogen, C1-C 20 Hydrocarbon groups, carboxyl groups (e.g., carboxylic acids, esters, amides, ketones, etc.), ethers, amino or hydroxyl groups.

[0032] In some embodiments, R3 and R4 may form a cyclic group. In some embodiments, the cyclic group includes one or more nitrogen atoms or one or more oxygen atoms.

[0033] R5 is C1-C 100 Hydrocarbon groups, carboxyl groups (e.g., carboxylic acids, esters, amides, ketones, etc.), ethers, or hydroxyl groups.

[0034] In one embodiment, R1 and R2 are both hydrogen. In some embodiments, at least one of R3 and R4 is a methyl group. In some embodiments, R5 is a C1-C4 hydrocarbon group.

[0035] Suitable examples of phenolamines include 1,3-bis((dimethylamino)methyl)naphth-2-ol (structure 2A), 2,4-bis(morpholinomethyl)naphth-1,3-diol (structure 2B), 5,7-bis((dimethylamino)methyl)quinoline-8-ol (structure 2C), 4,6-bis((dimethylamino)methyl)-1H-benzo[d]imidazol-5-ol (structure 2D) and 4-((dihexylamino)methyl)-1-phenyl-2-(phenylamino)-1H-benzo[d]imidazol-5-ol (structure 2E).

[0036]

[0037] The phenolic amine compositions of the present invention are commercially available or synthesized by any known method. For example, one or more phenolic amine additives of the present invention can be synthesized via the Mannich reaction, which typically involves the aminoalkylation of a carbonyl functional group by an aldehyde. A detailed description of the Mannich reaction can be found, for example, in U.S. Patent No. 7,351,864, which is incorporated herein by reference.

[0038] In some implementations, phenolamines can be present in salt form. The salts of phenolamines are typically in a protonated form (i.e., ammonium). When the phenolamine additive is present in salt form, it can cooperate with one or more minor LSPI-reducing additives. The interaction between the phenolamine and the minor additives is synergistic and can provide a greater LSPI reduction than expected.

[0039] In some embodiments, phenolamines may interact synergistically with one or more minor additives, wherein the phenolamines and one or more minor additives are in a non-salt (neutral) form. Suitable minor additives include acids (aliphatic acids, unsaturated acids, alkyl aromatic acids, aromatic acids, hydroxy acids, amino acids, salicylic acid), phenols, 1,3-dicarbonyl compounds (e.g., 1,3-diketones, 1,3-ketoesters), hydroxyamides, antioxidants (e.g., monocarboxylic acids, dicarboxylic acids), amidines, guanidines, and triazines.

[0040] The following is a description of minor additives that can be used as fuel or lubricant additives to reduce LSPI activity. Minor LSPI reducing additives, substituted minor LSPI reducing additives, or derivatives thereof will be used in their salt or neutral form and in combination with their salt or neutral form as a primary additive to reduce LSPI activity. For example, phenolic amines and aliphatic acids (minor additives) can be combined and used as LSPI additives.

[0041] Acid additives

[0042] aliphatic acids

[0043] Aliphatic acids are non-aromatic carboxylic acids. Suitable aliphatic acids include monocarboxylic acids with the following structures.

[0044]

[0045] R is an aliphatic group having 2 to 20 carbon atoms. The aliphatic group can be straight-chain or branched and may contain heteroatoms.

[0046] Suitable aliphatic acids include hexanoic acid (structure 3A), heptanoic acid (structure 3B), octanoic acid (structure 3C), nonanoic acid (structure 3D), decanoic acid (structure 3E), undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid (C). 20 ), behenic acid (C 22), 2-ethylbutyric acid (structure 3F), 3,3-dimethylbutyric acid, 2-methylvaleric acid (C6), 2-methylhexanoic acid (C7), 4-methylhexanoic acid (C7), 5-methylhexanoic acid (C7), 2,2-dimethylvaleric acid (C7), 2-propylvaleric acid (C8), 2-ethylhexanoic acid (structure 3G), 2-methylheptanoic acid (C8), isooctanoic acid (C8), 3,5,5-trimethylhexanoic acid (C9), 4-methyloctanoic acid (C9), 4-methylnonanoic acid (C9) 10 Isodecanoic acid (C) 10 ), 2-Butyloctanoic acid (C 12 ), isotriadecanoic acid (C 13 ), 2-hexyldecanoic acid (C 16 ), isopalmitic acid (C 16 ), isostearic acid (structure 3H), 3-cyclohexylpropionic acid, 4-cyclohexylbutyric acid (structure 3I), and cyclohexanepentanoic acid. Representative structures are shown below.

[0047]

[0048]

[0049] unsaturated acids

[0050] Suitable unsaturated acids include any organic acid containing carbon-carbon double or triple bonds. Representative unsaturated acids include maleic acid (structure 4A), fumaric acid (structure 4B), and unsaturated fatty acids such as palmitoleic acid (structure 4C) and oleic acid (structure 4D). Representative structures are shown below.

[0051]

[0052] Alkyl aromatic acids

[0053] Suitable alkyl aromatic acids include both monocarboxylic acids and dicarboxylic acids. Alkyl carboxylic acids may have six or more carbon atoms (e.g., 6 to 24 carbon atoms, 6 to 20 carbon atoms, 8 to 24 carbon atoms, 8 to 20 carbon atoms, or even 8 to 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 (structure 5A) and ethylbenzoic acid (structure 5B). Representative structures are shown below.

[0054]

[0055] aromatic acid

[0056] Suitable aromatic acids include both monocarboxylic acids and dicarboxylic acids. Alkyl carboxylic acids may have six or more carbon atoms (e.g., 6 to 24 carbon atoms, 6 to 20 carbon atoms, 8 to 24 carbon atoms, 8 to 20 carbon atoms, or even 8 to 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 aromatic acids include benzoic acid (structure 6A), hydroxybenzoic acid (structure 6B), and tetrahydronaphthalenecarboxylic acid (structure 6C). Representative structures are shown below.

[0057]

[0058] Hydroxy acids

[0059] Suitable hydroxy acids include those that can be represented by the following general formula:

[0060]

[0061] Where n = 1 to 3. Suitable examples of hydroxy acids include glycolic acid (structure 7A), lactic acid (structure 7B), malic acid (structure 7C), tartaric acid (structure 7D), and citric acid (structure 7E). Representative structures are shown below.

[0062]

[0063] Phenolic additives

[0064] phenol

[0065] Suitable phenols include thymol (structure 8A), eugenol (structure 8B), hydroquinone (structure 8C), resorcinol (structure 8D), p-cresol (structure 8E), 2-methylquinoline-8-ol ("8-hydroxyquinaidine") (structure 8G), phloroglucinol (structure 8H), m-cresol (structure 8I), o-cresol (structure 8J), catechol (structure 8K), and 8-quinolinol (structure 8L). Representative structures are shown below.

[0066]

[0067]

[0068] 1,3-Dicarbonyl Compound Additives

[0069] 1,3-Diketone

[0070] Suitable examples of 1,3-dione compounds include acetylacetone (structure 9A) and curcumin (structure 9B). Representative structures are shown below.

[0071]

[0072]

[0073] 1,3-keto esters

[0074] Suitable 1,3-keto esters are shown below.

[0075]

[0076] Hydroxyamide additives

[0077] Hydroxylamides are hydroxyl derivatives of amides. Useful hydroxyamides include those that can be represented by the following general formula:

[0078]

[0079] R1 and R2 are each independently selected from hydrogen or C1-C. 20 (For example, C3-C) 12 Alkyl groups. Suitable hydroxyamides include hydroxymethylacetamide (Formula 21A). Other suitable structures are shown below.

[0080]

[0081] Antioxidant additives

[0082] Suitable antioxidants include both monocarboxylic acids and dicarboxylic acids. Alkyl carboxylic acids may have six or more carbon atoms (e.g., 6 to 24 carbon atoms, 6 to 20 carbon atoms, 8 to 24 carbon atoms, 8 to 20 carbon atoms, or even 8 to 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 the following.

[0083]

[0084] Salicylic acid additives

[0085] salicylic acid

[0086] Suitable salicylic acids include 2-hydroxy-5-(tetracosyl-1,3,5,7,9,11,13,15,17,19,21,23-dodecyl-1-yl)benzoic acid-dihydro (structure 13E). Suitable salicylic acids are shown below.

[0087]

[0088]

[0089] amitraz

[0090] Useful amidons include those that can be expressed by the following general formula:

[0091]

[0092] R6, R7, R8, and R9 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (e.g., groups or portions containing nitrogen, oxygen, sulfur, or phosphorus, bonded by carbon atoms and lacking acidic functional groups such as carboxylic acid or sulfonic acid groups), and combinations thereof; and any two or more of R6, R7, R8, and R9 may optionally be bonded together to form a cyclic structure (e.g., a five-membered, six-membered, or seven-membered ring). The cyclic structure may be aromatic or non-aromatic, and may 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).

[0093] Suitable amidines include 1,4,5,6-tetrahydropyrimidine (structure 14A), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (structure 14B), 1,2-diethyl-1,4,5,6-tetrahydropyrimidine (structure 14C), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN; structure 14D), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU; structure 14E), benzylamidin (structure 14F), benzimidazole (structure 14G), and 2-phenyl-1H-benzi[d]imidazole (structure 14M). Representative structures are shown below.

[0094]

[0095] Guanidine additives

[0096] Representative examples of suitable guanidines include 1,1,3,3-tetramethylguanidine (structure 15A), 2-tert-butyl-1,1,3,3-tetramethylguanidine (structure 15B), phenylguanidine (structure 15C), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (structure 15D), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (structure 15E), 1,3-diphenylguanidine (structure 15F), 1,3-di-o-tolylguanidine (structure 15G), 1,2,3-triphenylguanidine (structure 15H), N-benzylguanidine (structure 15I), N-cyclohexylguanidine (structure 15J), aminoguanidine (structure 15K), 1,3-diaminoguanidine (structure 15L), N,N',N”-triaminoguanidine (structure 15M), and 1-phenylbiguanidine (structure 15N).

[0097]

[0098]

[0099] Triazine additives

[0100] Suitable triazines include N 2 N 4 N 6 -Triphenyl-1,3,5-triazine-2,4,6-triamine (structure 16A), 2,4,6-trimorpholino-1,3,5-triazine (structure 16B), 2,4,6-tris(4-methylpiperazin-1-yl)-1,3,5-triazine (structure 16C) and N 2 N 2 N 4 N 4 N 6 N 6 -Hexabutyl-1,3,5-triazine-2,4,6-triamine (structure 16D).

[0101]

[0102]

[0103] amino acids

[0104] Useful amino acids include those that can be represented by the following general formula:

[0105]

[0106] R represents an "aliphatic" or "aromatic" side chain. Amino acid side chains can be broadly classified as aromatic or aliphatic. Aromatic side chains consist of an aromatic ring. Examples of amino acids with aromatic side chains include, for example, histidine (structure 17A), phenylalanine (structure 17B), tyrosine (structure 17C), and tryptophan (structure 17D). Non-aromatic side chains are broadly grouped as "aliphatic" and include, for example, alanine (structure 17E), glycine (structure 17F), and cysteine ​​(structure 17G).

[0107] Amino acids can be natural and / or non-natural α-amino acids. Natural amino acids are those encoded by the genetic code, as well as amino acids derived from them. These include, for example, hydroxyproline (structure 17H), γ-carboxyglutamate (structure 17I), and citrulline (structure 17J). In this specification, the term "amino acid" also includes amino acid analogs and analytes. Analogs are compounds having the same general structure as natural amino acids, except that the R group is not found in natural amino acids.

[0108] Representative examples of naturally occurring amino acid analogs include homoserine (structure 17K), leucine (structure 17L), homoproline (structure 17M), and proline (structure 17N). Amino acid analogs are compounds with structures different from the general chemical structures of α-amino acids but with similar functions. The amino acid can be L- or D-amino acid. Suitable structures are shown below.

[0109]

[0110]

[0111] Salt

[0112] The salts disclosed herein can be prepared by conventional means, such as 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 typically mixed together in an approximately equimolar ratio. An excess of the primary or secondary additive component may be used. For example, the molar ratio of the base to the alkyl carboxylic acid may be from about 1.05:1 to 2:1 (e.g., 1.1:1 to 1.5:1).

[0113] fuel composition

[0114] The compounds disclosed herein can be used as additives in hydrocarbon fuels to prevent or reduce engine knocking or pre-ignition events in spark-ignition internal combustion engines.

[0115] The concentration of the compounds disclosed herein in hydrocarbon fuels can range from 25 to 5000 ppm by weight (e.g., 50 to 1000 ppm).

[0116] The compounds disclosed herein can be formulated into 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 higher-boiling aromatic compounds or aromatic diluents, can be used. Aliphatic alcohols containing 2 to 8 carbon atoms (such as ethanol, isopropanol, methyl isobutyl methanol, n-butanol, etc.) combined with hydrocarbon solvents are also suitable for use with the additives of this invention. In the concentrate, the amount of additive can range from 10% by weight to 70% by weight (e.g., 20% by weight to 40% by weight).

[0117] Other well-known additives may be used in gasoline fuels, including oxygenates (e.g., ethanol, methyl tert-butyl ether), other antiknock agents, and detergents / dispersants (e.g., hydrocarbon amines, hydrocarbon poly(oxyalkylene)amines, succinimides, Mannich reaction products, aromatic esters of polyalkylphenoxyalkanols, or polyalkylphenoxyaminoalkanes). Additionally, friction modifiers, antioxidants, metal passivators, and demulsifiers may be present.

[0118] Other well-known additives, such as pour point depressants, flow improvers, and cetane improvers, can be used in diesel fuel.

[0119] Fuel-soluble, non-volatile carrier fluids or oils may also be used with the compounds disclosed herein. The carrier fluid is a chemically inert, hydrocarbon-soluble liquid carrier that significantly increases the non-volatile residue (NVR) or solvent-free liquid fraction of the fuel additive composition without substantially increasing the octane requirement. The carrier fluid can be a natural or synthetic oil, such as mineral oil, refined petroleum, synthetic polyalkane and olefins, including hydrogenated and non-hydrogenated polyalphaolefins, synthetic polyoxyethylene-derived oils, such as those described in U.S. Patents 3,756,793, 4,191,537, and 5,004,478; and European Patent Application Publications 356,726 and 382,159.

[0120] 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 can be present in amounts ranging from 20% to 60% by weight (e.g., 30% to 50% by weight).

[0121] Lubricating oil composition

[0122] The compounds disclosed herein can be used as additives in lubricating oils to prevent or reduce engine knocking or pre-ignition events in spark-ignition internal combustion engines.

[0123] Based on the total weight of the lubricating oil composition, the concentration of the compounds of the present invention in the lubricating oil composition can be in the range of 0.01% by weight to 15% by weight (e.g., 0.5% by weight to 5% by weight).

[0124] A lubricating viscosity oil (sometimes referred to as a "base oil" or "base oil") is the main liquid component of a lubricant, into which additives and possibly other oils are blended, for example, to prepare the final lubricant (or lubricant composition). Base oils that can be used to prepare concentrates and, in turn, to prepare lubricant compositions from them, can be selected from natural (plant, animal, or mineral) and synthetic lubricants, as well as mixtures thereof.

[0125] The definitions of base oils and base oils in this disclosure are the same as those found in Appendix E of American Petroleum Institute (API) Publication 1509 (“API Guide to Base Oil Interchangeability for Passenger Car and Diesel Engine Oils,” December 2016). Group I base oils contain less than 90% saturation and / or more than 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1. Group II base oils contain greater than or equal to 90% saturation and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1. Group III base oils contain greater than or equal to 90% saturation and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 120 using the test methods specified in Table E-1. Group IV base oils are polyalphaolefins (PAO). Group V base oils include all other base oils not included in Groups I, II, III, or IV.

[0126] Natural oils include animal fats, 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 oils are preferred. The crude oil sources of mineral oils vary greatly; for example, they may be alkanes, cycloalkanes, or a mixture of alkane-cycloalkanes. Oils derived from coal or shale are also useful. The methods for producing and purifying natural oils also vary, for example, their distillation range and whether they are straight-run or cracked, hydrorefined or solvent-extracted.

[0127] Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils of polymerized and interpolymerized olefins (e.g., polybutene, polypropylene, propylene-isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alpha olefin copolymers). Polyalpha olefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oils. For example, oils derived from C8 to C999 can be used. 14 Olefins (e.g., C8, C6) 10 C 12 C 14 PAO (olefins or mixtures thereof).

[0128] Other useful fluids used as base oils include unconventional or non-conventional base oils that have been processed, preferably catalyzed, or synthesized to provide high-performance characteristics.

[0129] Unconventional or non-standard base oils / base oils include one or more mixtures of the following: base oils derived from one or more gas liquefaction (GTL) materials, and base oils derived from isomerization / dewaxing products of natural wax or waxy feedstocks, mineral and / or non-mineral oil waxy feedstocks (such as crude wax, natural wax) and waxy feedstocks (such as gas oil, waxy fuel hydrocracker bottom residue, waxy raffinate, hydrocracking products, thermal cracking products or other mineral, mineral oil), or even non-petroleum-derived waxy materials, such as waxy materials obtained from coal liquefaction or shale oil, and mixtures of such base oils.

[0130] The base oil used in the lubricating oil compositions of this disclosure is any one of various oils corresponding to API Group I, II, III, IV and V oils and mixtures thereof, preferably API Group II, III, IV and V oils and mixtures thereof, more preferably Group III to V base oils, because they have excellent volatility, stability, viscosity and cleanliness characteristics.

[0131] Typically, base oils will have a viscosity of 2.5 to 20 mm at 100°C. 2 / s (e.g., 3 to 12 mm) 2 / s, 4 to 10mm 2 / s or 4.5 to 8mm 2 kinematic viscosity (ASTM D445) per s.

[0132] The lubricating oil compositions of the present invention may also contain conventional lubricant additives for imparting auxiliary functions, to obtain a finished lubricating oil composition in which these additives are dispersed or dissolved. For example, the lubricating oil composition may be blended with antioxidants, ashless dispersants, anti-wear agents, detergents (such as metal detergents), rust inhibitors, defoamers, antiemulsifiers, friction modifiers, metal passivators, pour point depressants, viscosity modifiers, defoamers, cosolvents, packaging compatibility agents, corrosion inhibitors, dyes, extreme pressure agents, and mixtures thereof. Many additives are known and commercially available. These additives or similar compounds can be used to prepare the lubricating oil compositions of the present invention through a conventional blending process.

[0133] When used, each of the aforementioned additives is used in a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if the additive is an ashless dispersant, the functionally effective amount of that ashless dispersant will be sufficient to impart the desired dispersive properties to the lubricant. Generally, unless otherwise stated, when used, the concentration of each of these additives may range from about 0.001 wt% to about 20 wt% (e.g., from about 0.01 wt% to about 10 wt%).

[0134] The following illustrative examples are intended to be non-limiting.

[0135] Example

[0136] Engine testing

[0137] LSPI testing was conducted using a 4-GM 2.0-L Ecotec 4-cylinder gasoline turbocharged direct injection engine. In this setup, each cylinder was equipped with a pressure sensor to monitor in-cylinder pressure.

[0138] A six-segment test procedure was used to determine the number of LSPI events for all four cylinders at an engine speed of 2000 rpm and a load of 290 N-m. Each segment lasted 28 minutes, with an interval of idling time at low engine speed and load in between. The LSPI frequency during segments two through six was reported for comparison; and the first segment was disregarded due to engine oil conditioning. To account for LSPI activity under transient conditions, the beginning of each segment was filtered or removed to allow comparison only of activity during steady-state operation. This truncation typically resulted in the removal of approximately 4,000 cycles per cylinder per segment, resulting in approximately 100,000 measurement cycles per segment (or 25,000 cycles per cylinder).

[0139] During testing, combustion pressure and phase were monitored for each cylinder. An LSPI event occurred when two criteria were met: 1) peak cylinder pressure exceeded the average peak pressure by five standard deviations; and 2) combustion phase (CA5, or crank angle at 5% heat release) advanced by more than five standard deviations from the average CA5. Baseline LSPI activity was established before and after LSPI mitigation additive testing using additive-free 49th-state premium unleaded gasoline. Baseline fuel information: FR62180 - 49th-state additive-free PUL fuel. Engine oils used during testing conformed to ILSAC GF-5 and API SN specifications.

[0140] The LSPI frequency is reported as the average number of events per cylinder over one million cycles. The reported change in LSPI frequency is the percentage difference relative to pre-baseline and post-baseline runs.

[0141] In the examples shown below, the treatment rate is 1000 ppmw (1:1 equivalent) of additive in the fuel, wherein the primary additive is variable and the secondary additive is DBU.

[0142] The results of the LSPI event reduction are shown in Table 1 below.

[0143] Table 1

[0144]

[0145]

Claims

1. A fuel composition comprising: Hydrocarbon fuels with boiling points in the range of gasoline or diesel fuels; and The main additive or its salt having the structure given by the following formula ； Where A is the ring part; Where R1 and R2 are independently H and C1-C 20 Hydrocarbon groups, carboxylic acids, esters, amides, ketones, ethers, or hydroxyl groups; R3 and R4 are independently H and C1-C. 20 A hydrocarbon group, carboxylic acid, ester, amide, ketone, ether, amino or hydroxyl group, or wherein R3 and R4 are part of a cyclic group; R5 is C1-C 100 Hydrocarbon groups, carboxylic acids, esters, amides, ketones, ethers, or hydroxyl groups; and Where p is 0 to 2, n is 1 to 3, m is 1 to 3, and p+n+m is less than 5.

2. The composition of claim 1, wherein A is an aromatic ring or a heterocyclic ring.

3. The composition of claim 1, wherein the cyclic group comprises one or more nitrogen atoms or one or more oxygen atoms.

4. The composition of claim 1, further comprising: Secondary additives or their salts.

5. The composition of claim 4, wherein the minor additive is an acid, phenol, 1,3-dicarbonyl compound, hydroxyamide, antioxidant, amidine, or guanidine.

6. The composition of claim 4, wherein the minor additive is 2-ethylhexanoic acid or 1,8-diazabicyclo[5.4.0]-undecyl-7-ene.

7. The composition of claim 1, wherein R1 and R2 are both hydrogen.

8. The composition of claim 1, wherein at least one of R3 and R4 is an ethyl or butyl group.

9. A method for preventing or reducing low-speed pre-ignition events in a spark-ignition internal combustion engine, the method comprising: A fuel composition is supplied to the engine, the fuel composition comprising: Hydrocarbon fuels with boiling points in the range of gasoline; as well as The main additive or its salt having the structure given by the following formula ； Where A is the ring part; Where R1 and R2 are independently H and C1-C 20 Hydrocarbon groups, carboxylic acids, esters, amides, ketones, ethers, or hydroxyl groups; R3 and R4 are independently H and C1-C. 20 A hydrocarbon group, carboxylic acid, ester, amide, ketone, ether, amino or hydroxyl group, or wherein R3 and R4 are part of a cyclic group; R5 is C1-C 100 Hydrocarbon groups, carboxylic acids, esters, amides, ketones, ethers, or hydroxyl groups; and Where p is 0 to 2, n is 1 to 3, m is 1 to 3, and p+n+m is less than 5.

10. The method of claim 9, wherein the composition further comprises a minor additive or a salt thereof, wherein the minor additive is an acid, phenol, 1,3-dicarbonyl compound, hydroxyamide, antioxidant, amidine, or guanidine.

11. The method of claim 9, wherein A is an aromatic ring or a heterocyclic ring.

12. The method of claim 9, wherein the cyclic group comprises one or more nitrogen atoms or one or more oxygen atoms.

13. The method of claim 10, wherein the minor additive is 2-ethylhexanoic acid or 1,8-diazabicyclo[5.4.0]-undecyl-7-ene.

14. The method of claim 9, wherein R1 and R2 are both hydrogen.

15. The method of claim 9, wherein at least one of R3 and R4 is an ethyl or butyl group.

16. A lubricating oil composition comprising: Lubricating viscosity base oil; and The main additive or its salt having the structure given by the following formula ； Where A is the ring part; Where R1 and R2 are independently H and C1-C 20 Hydrocarbon groups, carboxylic acids, esters, amides, ketones, ethers, or hydroxyl groups; R3 and R4 are independently H and C1-C. 20 A hydrocarbon group, carboxylic acid, ester, amide, ketone, ether, amino or hydroxyl group, or wherein R3 and R4 are part of a cyclic group; R5 is C1-C 100 Hydrocarbon groups, carboxylic acids, esters, amides, ketones, ethers, or hydroxyl groups; and Where p is 0 to 2, n is 1 to 3, m is 2 to 3, and p + n + m is less than 5.

17. The composition of claim 16, further comprising a minor additive or a salt thereof, wherein the minor additive is an acid, phenol, 1,3-dicarbonyl compound, hydroxyamide, antioxidant, amidine, or guanidine.

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