Composition for mitigating pre-ignition events at low speeds
Phenolamine-based additives in fuels and lubricants address the challenge of stochastic pre-ignition in engines by reducing LSPI events, enhancing engine performance and safety.
Patent Information
- Application Number
- JP2025173132
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-03-31
- Filing Date
- 2025-10-14
- Publication Date
- 2026-02-10
AI Technical Summary
Turbocharged or supercharged engines experience stochastic pre-ignition (LSPI) events, causing severe knocking and potential engine damage, which are sporadic and difficult to identify and mitigate.
The use of phenolamine-based fuel and lubricant additives, optionally in combination with secondary additives, to prevent or minimize LSPI by incorporating them into the engine's fuel or lubricating oil, which can be synthesized through methods like the Mannich reaction.
The additives effectively reduce LSPI events, minimizing engine knocking and pre-ignition problems in high-pressure spark ignition internal combustion engines.
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Abstract
Description
[Technical Field]
[0001] The present disclosure relates to compositions and methods of using the compositions to prevent or mitigate low speed pre-ignition events in direct injection engines. [Background technology]
[0002] Turbocharged or supercharged engines (i.e., boosted internal combustion engines) can exhibit an abnormal combustion phenomenon known as stochastic pre-ignition or low-speed pre-ignition (i.e., "LSPI"). LSPI can result in high in-cylinder pressure and advanced combustion phasing, which can cause severe knocking intensity. In worst-case scenarios, LSPI can cause catastrophic engine damage. However, because LSPI events occur only sporadically and uncontrolled, identifying the cause of the phenomenon and developing solutions to mitigate it can be difficult.
[0003] One possible explanation for LSPI is that the event is caused, at least in part, by the spontaneous ignition of engine oil droplets that enter the engine combustion chamber through the piston gap under high pressure during periods when the engine is running at low speeds and the compression stroke is at its maximum.
[0004] Although new engine technologies, such as electronic controls and knock sensors, are being actively researched and developed to 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 hydrocarbon fuel boiling in the gasoline or diesel range; [ka] or a salt thereof, wherein A is a ring moiety, and R and R are independently H, C-C 20 a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group; R3 and R4 are independently H, C1-C 20 R3 and R4 are part of a cyclic group and R5 is a C1-C 100 It is a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group, p is 0 to 2, n is 1 to 3, m is 1 to 3, and p+n+m is less than 5.
[0006] In another aspect, a method for preventing or mitigating low speed pre-ignition events in a spark ignition internal combustion engine includes: [ka] or a salt thereof, wherein A is a ring moiety, and R and R are independently H, C-C 20 a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group; R3 and R4 are independently H, C1-C 20 R3 and R4 are part of a cyclic group and R5 is a C1-C 100 It is a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group, p is 0 to 2, n is 1 to 3, m is 1 to 3, and p+n+m is less than 5.
[0007] In yet another aspect, a base oil of lubricating viscosity; [ka] or a salt thereof, wherein A is a ring moiety, and R and R are independently H, C-C 20 a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group; R3 and R4 are independently H, C1-C 20 R3 and R4 are part of a cyclic group and R5 is a C1-C 100 It is a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group, p is 0 to 2, n is 1 to 3, m is 1 to 3, and p+n+m is less than 5. DETAILED DESCRIPTION OF THE INVENTION
[0008] overview As used herein, the following words and expressions have the meanings ascribed to them if and when used.
[0009] "Gasoline" or "gasoline boiling range constituents" means at least primarily C4-C 12 In one embodiment, gasoline or gasoline boiling range components refer to a composition containing at least primarily C4-C 12 It is further defined to mean a composition containing hydrocarbons and having a boiling point range of about 100°F (37.8°C) to about 400°F (204°C). In an alternative embodiment, gasoline or gasoline boiling range components are at least primarily C4-C6 12 It is defined to mean a composition containing hydrocarbons and having a boiling point range of about 100°F (37.8°C) to about 400°F (204°C), and further defined as meeting ASTM D4814.
[0010] The term "oil-soluble" means that, for a given additive, the amount required to impart the desired level of activity or performance can be incorporated by dissolving, dispersing, or suspending in an oil of lubricating viscosity. Typically, "oil-soluble" means that at least 0.001 wt. % of the additive can be incorporated into a lubricating oil composition. The term "fuel-soluble" is an analogy to an additive that is dissolved, dispersed, or suspended in a fuel.
[0011] The term "minor amount" is expressed with respect to the listed additive and with respect to the total weight of the composition and means less than 50% by weight of the composition calculated as the active ingredient of the additive.
[0012] An "engine" or "combustion engine" is a heat engine in which combustion of fuel occurs in a combustion chamber. An "internal combustion engine" is a heat engine in which combustion of fuel occurs in an enclosed space (the "combustion chamber"). A "spark ignition engine" is a heat engine in which combustion is ignited by a spark, usually from a spark plug. This is in contrast to a "compression ignition engine," usually a diesel engine, in which the heat generated by compression along with the injection of fuel is sufficient to initiate combustion without the need for external ignition.
[0013] Low Speed Pre-Ignition (LSPI) Low-speed pre-ignition (LSPI) is most likely, or more likely, to occur in direct-injection, boosted (turbocharged or supercharged), spark-ignition (gasoline) internal combustion engines that, during operation, produce brake mean effective pressures exceeding 1000 kPa (10 bar) at engine speeds between 1500 and 2500 rpm, e.g., 1500 and 2000 rpm. "Brake mean effective pressure" (BMEP) is defined as the amount of work accomplished during engine revolution, i.e., engine torque normalized by engine displacement, divided by the engine's swept volume. The term "brake" refers to the actual torque or power available at the engine flywheel, as measured by a dynamometer. BMEP is therefore a measure of the engine's useful energy output.
[0014] It has now been found that the fuel or lubricant additives of the present disclosure are particularly useful in high pressure spark ignition internal combustion engines, and when used in high pressure spark ignition internal combustion engines, prevent or minimize engine knocking and pre-ignition problems.
[0015] Phenolamine The fuel or lubricant additive of the present invention comprises a phenolamine composition having the following general structure 1, or a salt thereof: [ka] For Structure 1, n is 1 to 3, p is 0 to 2, and m is 1 to 3, where p+m+n<5.
[0016] The moiety A is a ring, such as an aromatic or heterocyclic ring.
[0017] Each R1 is independently hydrogen, C1-C 20 It may be a hydrocarbyl group, a carboxyl group (eg, a carboxylic acid, an ester, an amide, a ketone, etc.), an ether, or a hydroxyl group.
[0018] Each R2 is independently hydrogen, C1-C 20 It may be a hydrocarbyl group, a carboxyl group (eg, a carboxylic acid, an ester, an amide, a ketone, etc.), an ether, or a hydroxyl group.
[0019] Each R3 is independently hydrogen, C1-C 20 It may be a hydrocarbyl group, a carboxyl group (eg, carboxylic acid, ester, amide, ketone, etc.), an ether, amino, or a hydroxyl group.
[0020] Each R4 is independently hydrogen, C1-C 20 It may be a hydrocarbyl group, a carboxyl group (eg, carboxylic acid, ester, amide, ketone, etc.), an ether, amino, or a hydroxyl group.
[0021] In some embodiments, R3 and R4 can form a cyclic group. In some embodiments, the cyclic group contains one or more nitrogens or one or more oxygens.
[0022] R5 is C1-C 100 It may be a hydrocarbyl group, a carboxyl group (eg, a carboxylic acid, an ester, an amide, a ketone, etc.), an ether, or a hydroxyl group.
[0023] According to 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 hydrocarbyl group.
[0024] Suitable examples of phenolic amines include 1,3-bis((dimethylamino)methyl)naphthalene-2-ol (Structure 2A), 2,4-bis(morpholinomethyl)naphthalene-1,3-diol (Structure 2B), 5,7-bis((dimethylamino)methyl)quinolin-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). [ka]
[0025] The phenolamine compositions of the present invention can be commercially available or synthesized by any known method. For example, one or more phenolamine additives of the present invention can be synthesized by the Mannich reaction, which typically involves aminoalkylation of a carbonyl functional group with 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.
[0026] In some embodiments, the phenolamine can be present in a salt form. The salt of the phenolamine is typically in a protonated form (i.e., ammonium). When the phenolamine additive is present in a salt form, the additive can cooperate with one or more secondary LSPI-reducing additives. The interaction between the phenolamine and the secondary additive can be synergistic, resulting in a greater-than-expected reduction in LSPI.
[0027] In some embodiments, the phenolamine may interact synergistically with one or more secondary additives, where the phenolamine and the one or more secondary additives are in a non-salt (neutral) form. Suitable secondary additives include acids (fatty acids, unsaturated acids, alkylaromatic acids, aromatic acids, hydroxy acids, amino acids, salicylic acids), phenols, 1,3-dicarbonyls (e.g., 1,3-diketones, 1,3-ketoesters), hydroxyamides, antioxidants (e.g., monocarboxylic acids, dicarboxylic acids), amidines, guanidines, and triazines.
[0028] The following is a description of secondary additives that can be used as fuel or lubrication additives to reduce LSPI activity. Secondary LSPI-reducing additives, substituted secondary LSPI-reducing additives, or derivatives thereof, can be used in their salt or neutral forms and in combination with a salt or neutral form of a primary additive to reduce LSPI activity. For example, a phenolamine and a fatty acid (secondary additive) can be combined and used as an LSPI additive.
[0029] Acid Additive fatty acid Fatty acids are non-aromatic carboxylic acids. Suitable fatty acids include monocarboxylic acids having the following structure: [ka] wherein R is an aliphatic group having 2 to 20 carbon atoms. The aliphatic group may be straight or branched chain and may contain heteroatoms.
[0030] Suitable fatty 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, arachidic acid (Structure 3C), and the like. 20 ), behenic acid (C 22 ), 2-ethylbutyric acid (Structure 3F), 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 (Structure 3G), 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 (structure 3H), 3-cyclohexylpropionic acid, 4-cyclohexylbutyric acid (structure 31), and cyclohexanepentanoic acid. Exemplary structures are shown below. [ka]
[0031] unsaturated acid Suitable unsaturated acids include any organic acid containing double or triple carbon-carbon bonds. Exemplary 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). Exemplary structures are shown below. [ka]
[0032] Alkyl aromatic acids Suitable alkylaromatic acids include both monocarboxylic and dicarboxylic acids. The alkylcarboxylic acid can have 6 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 portion may optionally be substituted with one or more substituents, such as hydroxy, alkoxy, and carbonyl (e.g., aldehyde or ketone) groups. Suitable examples of alkylaromatic acids include methylbenzoic acid (Structure 5A) and ethylbenzoic acid (Structure 5B). Exemplary structures are shown below. [ka]
[0033] aromatic acid Suitable aromatic acids include both monocarboxylic and dicarboxylic acids. The alkyl carboxylic acid can have 6 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 portion 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 (Structure 6A), hydroxybenzoic acid (Structure 6B), and tetralin carboxylic acid (Structure 6C). Exemplary structures are shown below. [ka]
[0034] hydroxy acids Suitable hydroxy acids include those that can be represented by the following general formula: [ka] wherein 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). Exemplary structures are shown below. [ka]
[0035] phenolic additives phenol Suitable phenols include thymol (Structure 8A), eugenol (Structure 8B), hydroquinone (Structure 8C), resorcinol (Structure 8D), p-cresol (Structure 8E), 2-methylquinolin-8-ol ("8-hydroxyquinaldine") (Structure 8G), phloroglucinol (Structure 8H), m-cresol (Structure 8I), orthocresol (Structure 8J), catechol (Structure 8K), and 8-quinolinol (Structure 8L). Exemplary structures are shown below. [ka]
[0036] 1,3-Dicarbonyl Additives 1,3-diketone Suitable examples of 1,3-diketone compounds include acetylacetone (Structure 9A) and curcumin (Structure 9B). Exemplary structures are shown below. [ka]
[0037] 1,3-ketoester Suitable 1,3-ketoesters are shown below. [ka]
[0038] Hydroxamide Additives Hydroxamides are hydroxy derivatives of amides. Useful hydroxamides include those that can be represented by the following general formula: [ka] wherein R1 and R2 are each independently hydrogen or C1-C 20 (e.g., C3-C 12 ) alkyl groups. Suitable hydroxamides include hydroxymethylacetamide (Formula 21A). Other suitable structures are shown below: [ka]
[0039] Antioxidant Additives Suitable antioxidants include both monocarboxylic and dicarboxylic acids. The alkyl carboxylic acid can have 6 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 portion may optionally be substituted with one or more substituents such as hydroxy, alkoxy, and carbonyl (e.g., aldehyde or ketone) groups. Suitable antioxidants include: [ka]
[0040] Salicylic Acid Additives Salicylic acid Suitable salicylic acids include 2-hydroxy-5-(tetracosa-1,3,5,7,9,11,13,15,17,19,21,23-dodecayn-1-yl)benzoic acid-dihydrogen (Structure 13E). Suitable salicylic acids are shown below. [ka]
[0041] Amidine Useful amidines include those that can be represented by the following general formula: [ka] wherein R6, R7, R8, and R9 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups (e.g., containing nitrogen, oxygen, sulfur, or phosphorus in the form of a group or moiety bonded via a carbon atom and not containing an acidic functional group such as carboxyl or sulfone), and combinations thereof; any two or more of R6, R7, R8, and R9 can optionally be bonded to each other to form a cyclic structure (e.g., a five-, six-, or seven-membered ring). The cyclic structure can be aromatic or non-aromatic and, in addition, can vary from fully saturated to fully unsaturated. The organic and heteroorganic groups can have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms).
[0042] 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), benzamidine (Structure 14F), benzimidazole (Structure 14G), and 2-phenyl-1H-benzo[d]imidazole (Structure 14M). Exemplary structures are shown below. [ka]
[0043] Guanidine Additive 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, guanidine (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-phenylbiguanide (Structure 15N). [ka] [ka] Triazine Additives
[0044] 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). [ka]
[0045] amino acid Useful amino acids include those that can be represented by the following general formula: [ka] wherein R is an "aliphatic" or "aromatic" side chain. Amino acid side chains can be broadly classified as aromatic or aliphatic. Aromatic side chains include aromatic rings. Examples of amino acids with aromatic side chains include, for example, histidine (Structure 17A), phenylalanine (Structure 17B), tyrosine (Structure 17C), tryptophan (Structure 17D), etc. Non-aromatic side chains are broadly classified as "aliphatic" and include, for example, alanine (Structure 17E), glycine (Structure 17F), cysteine (Structure 17G), etc.
[0046] The amino acid(s) can be natural and / or unnatural alpha amino acids. Natural amino acids are those encoded by the genetic code, as well as amino acids derived therefrom. These include, for example, hydroxyproline (structure 17H), gamma-carboxyglutamate (structure 17I), and citrulline (structure 17J). As used herein, the term "amino acid" also includes amino acid analogs and mimetics. Analogs are compounds that have the same general structure as a natural amino acid, except that the R group is one not found in natural amino acids.
[0047] Representative examples of analogs of naturally occurring amino acids include homoserine (structure 17K), norleucine (structure 17L), homoproline (structure 17M), and proline (structure 17N). Amino acid mimetics are compounds that have a structure that differs from the general chemical structure of alpha amino acids but function similarly to alpha amino acids. Amino acids can be L- or D-amino acids. Suitable structures are shown below. [ka] [ka]
[0048] salt The salts of the present 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 critical. The primary additive and the secondary additive are usually mixed together in approximately equal molar ratios. An excess of the primary or secondary additive components may be used. For example, the molar ratio of base to alkylcarboxylic acid may be about 1.05:1 to 2:1 (e.g., 1.1:1 to 1.5:1).
[0049] fuel composition The compounds of the present disclosure can be used as additives in hydrocarbon fuels to prevent or mitigate engine knock or pre-ignition events in spark-ignition internal combustion engines.
[0050] The concentration of the compounds of the present disclosure in hydrocarbon fuels may range from 25 to 5000 parts per million by weight (eg, 50 to 1000 ppm).
[0051] The compounds of the present disclosure can be formulated as concentrates using inert, stable, lipophilic (i.e., soluble in hydrocarbon fuel) organic solvents boiling 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, may be used. Aliphatic alcohols containing 2 to 8 carbon atoms, such as ethanol, isopropanol, methyl isobutyl carbinol, n-butanol, and the like, in combination with hydrocarbon solvents are also suitable for use with the present additives. In concentrates, the amount of additive may be 10 to 70 wt. % (e.g., 20 to 40 wt. %).
[0052] In gasoline fuels, other well-known additives can be used, including oxygenates (e.g., ethanol, methyl tert-butyl ether), other antiknock agents, and detergent / dispersants (e.g., hydrocarbyl amines, hydrocarbyl poly(oxyalkylene) amines, succinimides, Mannich reaction products, aromatic esters of polyalkylphenoxyalkanols, or polyalkylphenoxyaminoalkanes). Additionally, friction modifiers, antioxidants, metal deactivators, and demulsifiers may be present.
[0053] Other well-known additives may be used in diesel fuels, such as pour point depressants, flow improvers, cetane improvers, and the like.
[0054] Fuel-soluble, nonvolatile carrier fluids or oils may also be used with the compounds of the present disclosure. Carrier fluids are chemically inert, hydrocarbon-soluble liquid vehicles that somewhat contribute to increasing the octane requirement, but substantially increase the nonvolatile residue (NVR) or solvent-free fluid fraction of the fuel additive composition. Carrier fluids may be natural or synthetic oils, such as mineral oils, refined petroleum oils, synthetic polyalkanes and alkenes, including hydrogenated and non-hydrogenated polyalphaolefins, synthetic polyoxyalkylene-derived oils, such as those described in U.S. Pat. Nos. 3,756,793; 4,191,537; and 5,004,478; and European Patent Publication Nos. 356,726 and 382,159.
[0055] Carrier fluids may be used in amounts ranging from 35 to 5,000 ppm by weight of the hydrocarbon fuel (e.g., 50 to 3,000 ppm of the fuel). When used in a fuel concentrate, the carrier fluid may be present in an amount ranging from 20 to 60% by weight (e.g., 30 to 50% by weight).
[0056] lubricating oil composition The compounds of the present disclosure can be used as additives in lubricating oils to prevent or mitigate engine knock or pre-ignition events in spark-ignition internal combustion engines.
[0057] The concentration of the compounds of the present disclosure in the lubricating oil composition may range from 0.01 to 15 wt % (eg, 0.5 to 5 wt %), based on the total weight of the lubricating oil composition.
[0058] An oil of lubricating viscosity (sometimes referred to as a "base stock" or "base oil") is the primary liquid constituent of a lubricant into which additives and possibly other oils are blended to produce, for example, the final lubricant (or lubricant composition). Base oils useful for making concentrates and for making lubricating oil compositions therefrom may be selected from natural (vegetable, animal, or mineral) and synthetic lubricating oils and mixtures thereof.
[0059] The definitions of base stock and base oil in this disclosure are the same as those set forth 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% saturates and / or more than 0.03% sulfur and have a viscosity index of 80 or greater and less than 120, using the test methods set forth in Table E-1. Group II base stocks contain 90% or greater saturates and 0.03% or less sulfur and have a viscosity index of 80 or greater and less than 120, using the test methods set forth in Table E-1. Group III base stocks contain 90% or greater saturates and 0.03% or less sulfur and have a viscosity index of 120 or greater, using the test methods set forth in Table E-1. Group IV base stocks are polyalphaolefins (PAOs). Group V base stocks include all other base stocks not included in Group I, II, III, or IV.
[0060] Natural oils include animal oils, vegetable oils (e.g., castor oil and lard oil), and mineral oils. Animal and vegetable oils with favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely in terms of their crude source, for example, whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils also vary in terms of the methods used to produce and refine them, for example, their distillation range and whether they are straight-run, cracked, hydrorefined, or solvent extracted.
[0061] Synthetic oils include hydrocarbon oils, such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymer, ethylene-olefin copolymer, and ethylene-alphaolefin copolymer). Polyalphaolefin (PAO) oil base stocks are commonly used for synthetic hydrocarbon oils. Examples include C8 to C 14 Olefins, e.g., C8, C 10 , C 12 , C 14 PAOs derived from olefins, or mixtures thereof may also be utilized.
[0062] Other useful fluids for use as base oils include non-conventional or unconventional base stocks that are preferably catalytically treated or synthetically processed to provide high performance properties.
[0063] Non-conventional or unconventional base stocks / base oils include one or more of a mixture of base stock(s) derived from one or more natural gas to liquids (GTL) materials, as well as isomerized / isodewaxed base stock(s) derived from natural wax or waxy feedstocks, mineral and / or non-mineral oil waxy feedstock stocks such as slack wax, natural wax, and waxy stocks such as gas oil, waxy fuel hydrocracker bottoms, waxy raffinate, hydrocracket, thermal crackate, or other mineral, mineral oil, as well as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks.
[0064] Base oils for use in the lubricating oil compositions of the present disclosure are any of the 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 the various oils corresponding to Group III through Group V base oils due to their superior volatility, stability, viscosity properties and cleanliness characteristics.
[0065] Typically, the base oil is 2.5 to 20 mm 2 / sec (e.g., 3 to 12 mm 2 / sec, 4~10mm 2 / sec, or 4.5 to 8 mm 2 It has a kinematic viscosity (ASTM D445) at 100°C in the range of 1 / sec.
[0066] The lubricating oil composition may also contain conventional lubricant additives to provide auxiliary functions, resulting in the finished lubricating oil composition being dispersed or dissolved in these additives. For example, the lubricating oil composition may be blended with antioxidants, ashless dispersants, antiwear agents, detergents such as metal detergents, rust inhibitors, deodorizers, demulsifiers, friction modifiers, metal deactivators, pour point depressants, viscosity modifiers, antifoam agents, cosolvents, package compatibility agents, corrosion inhibitors, dyes, extreme pressure agents, etc., and mixtures thereof. Various additives are known and commercially available. These additives, or their analogous compounds, can be used to prepare the lubricating oil composition of the present invention by conventional blending procedures.
[0067] Each of the foregoing additives, when used, 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, a functionally effective amount of the ashless dispersant is an amount sufficient to impart the desired dispersant characteristics to the lubricant. Generally, the concentration of each of these additives may range from about 0.001 to about 20% by weight, e.g., from about 0.01 to about 10% by weight, unless otherwise specified.
[0068] The following illustrative examples are intended to be non-limiting. [Example]
[0069] Engine Test The LSPI test was performed using a 4-GM 2.0-L Ecotex 4-cylinder gasoline turbocharged direct injection engine. In this setup, each cylinder was fitted with a pressure transducer to monitor the in-cylinder pressure.
[0070] A six-segment test procedure was used to measure the number of LSPI events across all four cylinders at an engine speed of 2000 rpm and a load of 290 N-m. Each segment was 28 minutes long and separated by an idle period at low engine speed and load. LSPI frequencies in segments 2 through 6 are reported for comparison; the first segment is not considered due to engine oil conditioning. To account for LSPI activity during transient conditions, the beginning of each segment was filtered or removed, allowing comparison of activity only during steady-state operation. This separation typically removes approximately 4,000 cycles per cylinder per segment, resulting in 100,000 measurement cycles per segment (or 25,000 cycles per cylinder).
[0071] Both combustion pressure and phasing were monitored for each cylinder during testing. An LSPI event occurred when two criteria were met: 1) peak cylinder pressure exceeded five standard deviations from the average peak pressure; and 2) combustion phasing (CA5, or the crank angle at which 5% heat release occurs) advanced more than five standard deviations from the average CA5. Unadulterated 49-state premium unleaded gasoline was used to establish baseline LSPI activity before and after LSPI mitigation additive testing. Baseline fuel information: FR62180-49 state unadulterated PUL fuel. The engine oil used during testing met ILSAC GF-5 and API SN specifications.
[0072] LSPI frequency is reported as the average number of events per cylinder over 1 million cycles. Reported changes in LSPI frequency are the percentage difference from pre- and post-run baseline.
[0073] The treat rate in the examples below is 1000 ppmw (1:1 equivalent) additive in fuel, the primary additive is various, and the secondary additive is DBU. The results of the reduction in LSPI events are shown in Table 1 below. [Table 1-1] Table 1-2
Claims
1. a hydrocarbon fuel boiling in the gasoline or diesel range; 【Chemistry 1】 or a salt thereof; and a fuel composition comprising: wherein A is a ring moiety; R １ and R ２ are independently H, C １ -C ２０ is a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group; R ３ and R ４ are independently H, C １ -C ２０ a hydrocarbyl group, a carboxyl group, an ether, an amino, or a hydroxyl group, or R ３ and R ４ is part of a cyclic group, and R ５ is C １ -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.
2. The composition of claim 1 , wherein the carboxyl group is a carboxylic acid, ester, amide, or ketone.
3. The composition of claim 1 , wherein A is an aromatic ring or a heterocyclic ring.
4. The composition of claim 1 , wherein the cyclic group comprises one or more nitrogens or one or more oxygens.
5. The composition of claim 1 further comprising a secondary additive or a salt thereof.
6. The composition of claim 5, wherein the secondary additive is an acid, a phenol, a 1,3-dicarbonyl, a hydroxyamide, an antioxidant, a salicylate, an amidine, or a guanidine.
7. The composition of claim 5, wherein the secondary additive is 2-ethylhexanoic acid or 1,8-diazabicyclo[5.4.0]-undec-7-ene.
8. R １ and R ２ The composition of claim 1 wherein both are hydrogen.
9. R ３ and R ４ The composition of claim 1 , wherein at least one of is an ethyl or butyl group.
10. 1. A method for preventing or mitigating low speed pre-ignition events in a spark ignition internal combustion engine, comprising: a hydrocarbon fuel boiling in the gasoline or diesel range; 【Chemistry 2】 or a salt thereof. wherein A is a ring moiety; R １ and R ２ are independently H, C １ -C ２０ is a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group; R ３ and R ４ are independently H, C １ -C ２０ a hydrocarbyl group, a carboxyl group, an ether, an amino, or a hydroxyl group, or R ３ and R ４ is part of a cyclic group, and R ５ is C １ -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.
11. 11. The method of claim 10, wherein the composition further comprises a secondary additive or a salt thereof, the secondary additive being an acid, a phenol, a 1,3-dicarbonyl, a hydroxyamide, an antioxidant, a salicylate, an amidine, or a guanidine.
12. The method of claim 10, wherein the carboxyl group is a carboxylic acid, an ester, an amide, or a ketone.
13. 11. The method of claim 10, wherein A is an aromatic ring or a heterocyclic ring.
14. The method of claim 10 , wherein the cyclic group comprises one or more nitrogens or one or more oxygens.
15. 12. The method of claim 11, wherein the secondary additive is 2-ethylhexanoic acid or 1,8-diazabicyclo[5.4.0]-undec-7-ene.
16. R １ and R ２ The method of claim 10 , wherein both are hydrogen.
17. R ３ and R ４ The method of claim 10, wherein at least one of is an ethyl or butyl group.
18. 1. A lubricating oil composition comprising: a base oil having a lubricating viscosity; 【Transformation 3】 or a salt thereof. wherein A is a ring moiety; R １ and R ２ are independently H, C １ -C ２０ is a hydrocarbyl group, a carboxyl group, an ether, or a hydroxyl group; R ３ and R ４ are independently H, C １ -C ２０ a hydrocarbyl group, a carboxyl group, an ether, an amino, or a hydroxyl group, or R ３ and R ４ is part of a cyclic group, and R ５ is C １ -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.
19. 19. The composition of claim 18, further comprising a secondary additive or a salt thereof, wherein the secondary additive is an acid, a phenol, a 1,3-dicarbonyl, a hydroxyamide, an antioxidant, a salicylate, an amidine, or a guanidine.
20. 19. The composition of claim 18, wherein the carboxyl group is a carboxylic acid, ester, amide, or ketone.