CN113227332B - Compositions and methods for preventing or reducing low-speed preignition in spark-ignited internal combustion engines - Google Patents

Abstract

Disclosed herein is a fuel composition comprising: (1) Greater than 50 weight percent of a hydrocarbon fuel having a boiling point in the gasoline or diesel range, and (2) a small amount of a low velocity pre-ignition (LSPI) reducing additive comprising one or more of an amidine or a beta-aminoalkanol having the structure wherein R is ₁ 、R ₂ 、R ₃ And R is ₄ Each independently selected from hydrogen, aromatic ring and C ₁ ‑C ₂₀ Alkyl, and R ₅ Is hydrogen or has the structure- (CH) R ₆ Alcohols of-OH, R ₆ Is hydrogen, C ₁ ‑C ₁₀ Alkyl or C ₁ ‑C ₁₀ Alkenyl:

Description

Composition and method for preventing or reducing low speed pre-ignition in spark ignition internal combustion engines

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of co-pending U.S. Patent Application Serial No. 16/362,157, filed on March 22, 2019, entitled “COMPOSITION AND METHOD FOR PREVENTING OR REDUCING LOW SPEED PRE-IGNITION IN SPARK-IGNITED INTERNAL COMBUSTION ENGINES,” which claims the benefit of U.S. Provisional Patent Application No. 62/647,186, filed on March 23, 2018, entitled “COMPOSITION AND METHOD FOR PREVENTING OR REDUCING LOW SPEED PRE-IGNITION IN SPARK-IGNITED INTERNAL COMBUSTION ENGINES,” and U.S. Provisional Patent Application No. 62/647,186, filed on November 15, 2018, entitled “COMPOSITION AND METHOD FORPREVENTING OR REDUCING LOW SPEED PRE-IGNITION IN SPARK-IGNITED INTERNAL COMBUSTION ENGINES.” ENGINES” which is incorporated herein by reference.

Technical Field

The present disclosure relates to fuel and lubricant compositions for spark-ignition engines and methods of using the same to prevent or reduce low speed pre-ignition events.

background

Turbocharged or supercharged engines (i.e., supercharged internal combustion engines) may experience an abnormal combustion phenomenon known as random pre-ignition or low speed pre-ignition (or "LSPI"). LSPI is an event that can include very high pressure spikes, pre-ignition occurring during inappropriate crankshaft angles, and knock. All of these, individually and in combination, can cause engine degradation and/or severe damage. However, because LSPI events occur only occasionally in an uncontrolled manner, it is difficult to identify the cause of this phenomenon and to develop solutions to curb it.

Pre-ignition is a form of combustion that causes the air-fuel mixture in the combustion chamber to burn before the desired ignition of the air-fuel mixture by the igniter. Pre-ignition is typically a problem during high engine load operation because the heat generated by the engine operation heats a portion of the combustion chamber to a temperature sufficient to ignite the air-fuel mixture upon contact. This type of pre-ignition is sometimes called hot spot pre-ignition.

Recently, intermittent abnormal combustion has been observed in supercharged internal combustion engines at low speeds and medium to high loads. For example, low speed pre-ignition (LSPI) may occur in a random and random manner during engine operation at 3,000 rpm or less, low load, and at least 10 bar brake mean effective pressure (BMEP). During low speed engine operation, the compression stroke time is longest.

Previous studies have shown that turbocharger use, engine design, engine coatings, piston geometry, fuel selection, and/or oil additives may contribute to an increase in LSPI events. Therefore, there is a need for fuel and oil additive components and/or combinations that effectively reduce or eliminate LSPI.

summary

In one aspect, a fuel composition is provided, comprising: (1) greater than 50 weight percent of a hydrocarbon fuel having a boiling point in the gasoline or diesel range, and (2) a small amount of a low speed pre-ignition (LSPI) reducing additive, the additive comprising one or more of an amidine or a β-aminoalkanol having the following structure or a salt thereof:

wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, an aromatic ring and a C ₁ -C ₂₀ alkyl group, and R ₅ is hydrogen or an alcohol having the structure —(CH)R ₆ —OH, wherein R ₆ is hydrogen, a C ₁ -C ₁₀ alkyl group, or a C ₁ -C ₁₀ alkenyl group.

In another aspect, a fuel concentrate is provided, comprising: (1) 90 to 30 weight percent of an organic solvent having a boiling point of 65° C. to 205° C., and (2) 10 to 70 weight percent of an additive component, the additive component comprising one or more of an amidine or a β-aminoalkanol having the following structure or a salt thereof:

wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, an aromatic ring and a C ₁ -C ₂₀ alkyl group, and R ₅ is hydrogen or an alcohol having the structure —(CH)R ₆ —OH, wherein R ₆ is hydrogen, a C ₁ -C ₁₀ alkyl group, or a C ₁ -C ₁₀ alkenyl group.

In another aspect, a method for reducing low speed pre-ignition events in an engine is provided, the method comprising (1) greater than 50 weight percent of a hydrocarbon fuel having a boiling point in the gasoline or diesel range and (2) a small amount of a low speed pre-ignition (LSPI) reducing additive, the additive comprising one or more of a triazole, an amidine, or a β-aminoalkanol having the following structure or a salt thereof:

wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen and C ₁ -C ₂₀ alkyl, and R ₅ is hydrogen or an alcohol having the structure —(CH)R ₆ —OH, wherein R ₆ is hydrogen, C ₁ -C ₁₀ alkyl, or C ₁ -C ₁₀ alkenyl.

Detailed description

introduce

In this specification, if the following words and expressions are used, they have the meanings given below.

"Gasoline" or "gasoline boiling range components" refers to a composition comprising at least primarily C4- _C12 hydrocarbons. In one embodiment, gasoline or gasoline boiling range components are further defined to mean a composition comprising at least primarily _C4 - _{C12 hydrocarbons} and having a boiling 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 defined to mean a composition comprising at least primarily _C4 - _C12 hydrocarbons, having a boiling range of about 100°F (37.8°C) to about 400°F (204°C), and are further defined in accordance with ASTM D4814.

The term "diesel" refers to a middle distillate fuel that contains at least primarily _C10 -C25 hydrocarbons. In one embodiment, diesel is further defined as a composition that contains at least primarily _C10 - _{C25 hydrocarbons} and has a boiling range of about 165.6°C (330°F) to about 371.1°C (700°F). In an alternative embodiment, diesel is defined as above, refers to a composition that contains at least primarily _C10 - _C25 hydrocarbons and has a boiling range of about 165.6°C (330°F) to about 371.1°C (700°F), and is further defined as conforming to ASTM D975.

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 of 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 an additive that is dissolved, dispersed or suspended in a fuel.

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

An "alkanol" is an alkyl group as described herein having a hydroxy substituent (ie, an -OH group).

"Minor amount" means less than 50% by weight of the composition, expressed relative to the additive and relative to the total weight of the composition, and is considered to be the active ingredient of the additive.

An "analog" is a compound that has a structure similar to another compound but differs from that compound in that some component, such as one or more atoms, functional groups, substructures, is replaced by another atom, group, or substructure.

"Homologs" are compounds that belong to a series of compounds that differ from each other by a repeating unit. Alkanes are examples of homologs. For example, ethane and propane are homologs because they differ only in the length of the repeating unit ( _-CH2- ). Homologs can be considered specific types of analogs.

A "derivative" is a compound that is derived from a similar compound via a chemical reaction (e.g., an acid-base reaction, hydrogenation, etc.). In the context of a substituent, 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. One of ordinary skill in the relevant art will know the boundaries of what is considered a derivative. The term "substituted" refers to a substitution or replacement of one or more atoms of a compound. As an illustrative example, "substituted alkyl" refers in particular to ethanol.

An "engine" or "combustion engine" is a heat engine in which the combustion of the fuel occurs within a combustion chamber. An "internal combustion engine" is a heat engine in which the combustion of the fuel occurs in a confined 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" (typically a diesel engine), in which the heat generated by compression together with the injection of fuel is sufficient to initiate combustion without an external spark.

Low Speed Pre-Ignition (LSPI)

Low speed pre-ignition (LSPI) is most likely to occur in direct injection, supercharged (turbocharged or supercharged with a supercharger), spark ignition (gasoline) internal combustion engines that, when operating, produce a brake mean effective pressure greater than 1000 kPa (10 bar) at engine speeds of 1500 to 2500 revolutions per minute (rpm), such as at engine speeds of 1500 to 2000 rpm. "Brake Mean Effective Pressure" (BMEP) is defined as the work done during an engine cycle divided by the engine displacement, normalizing the engine torque by the engine displacement. The word "brake" refers to the actual torque or power available at the engine flywheel as measured on a dynamometer. Therefore, BMEP is a measure of the useful energy output of the engine.

It has now been discovered that the fuel composition or lubricating oil composition of the present disclosure is particularly suitable for use in high pressure spark ignition internal combustion engines and, when used in high pressure spark ignition internal combustion engines, will prevent or minimize engine knock and pre-ignition problems.

Main additives to reduce LSPI

The following is a description of primary additives that can be used as fuel or lubricant additives to reduce LSPI activity. Primary additives that reduce LSPI can be used as stand-alone additives and/or in conjunction with other primary additives and/or one or more secondary additives that reduce LSPI (described later). When more than one additive is used, the additives can be in salt form. In addition, when two or more additives are used, there may be a synergistic effect between the two or more additives. Typically, these additives are soluble in the fuel or oil at the concentrations required to achieve the desired level of LSPI reduction. Table 1 summarizes the primary additive types.

Table 1

1. Amino additives

β-Aminoalkanol

The fuel additive or lubricating oil additive of the present disclosure can be a β-aminoalkanol, a substituted β-aminoalkanol, a derivative thereof or an acceptable salt thereof. Useful β-aminoalkanols include those that can be represented by the following general formula:

Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently selected from hydrogen and C ₁ -C ₂₀ alkyl (e.g., C ₁ -C ₆ alkyl); two or more of R ₁ , R ₂ , R ₃ , and R ₄ may be optionally combined together to form a ring structure (e.g., a five-membered, six-membered, or seven-membered ring). In some embodiments, R ₁ , R ₂ , R ₃ , and R ₄ may independently include one or more aromatic rings. R ₅ is hydrogen or an alcohol having the structure –(CH)R ₆ -OH, wherein R ₆ is hydrogen, C ₁ -C ₁₀ alkyl, or C ₁ -C ₁₀ alkenyl. In some embodiments, R ₅ is hydrogen. In some embodiments, R ₅ is an alcohol having the structure –(CH)R ₆ -OH, wherein R ₆ is hydrogen, C ₁ -C ₁₀ alkyl, or C ₁ -C ₁₀ alkenyl.

In an embodiment, the beta-aminoalkanol is not:

In certain embodiments, the fuel composition does not include:

In certain embodiments, the fuel concentrate does not contain:

In certain embodiments, the beta-aminoalkanol used in the method of reducing low speed pre-ignition events in an engine is not:

In certain embodiments, the low speed pre-ignition (LSPI) reducing additive does not include:

In an embodiment, the amino alcohol is not:

The β-aminoalkanol has at least 2 carbon atoms (e.g., 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).

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), cycloleucin (Formula 1L), cycloleucin (Formula 1C), cycloleucin (Formula 1D), cycloleucin (Formula 1E), cycloleucin (Formula 1F), cycloleucin (Formula 1G), 2-amino-1-pentanol (Formula 1H), valinol (Formula 1I), 2-amino-1-hexanol (Formula 1J), leucinol (Formula 1K), isoleucinol (Formula 1L), cycloleucin (Formula 1L), cycloleucin (Formula 1 In some embodiments, the β-aminoalkanol is aminoheptylpropanediol (3-(heptane-2-ylamino)propane-1,2-diol) (Formula 1T), aminooctylpropanediol (3-(methyl(octyl)amino)propane-1,2-diol) (Formula 1U), and aminododecylethanol (2-(methyl(dodecyl)amino)ethan-1-ol) (Formula 1V). In some embodiments, the β-aminoalkanol is aminoheptylpropanediol (3-(heptane-2-ylamino)propane-1,2-diol) (Formula 1T). In some embodiments, the β-aminoalkanol is aminooctylpropanediol (3-(methyl(octyl)amino)propane-1,2-diol) (Formula 1U). In certain embodiments, the β-aminoalkanol is aminododecylethanol (2-(dodecyl(methyl)amino)ethan-1-ol) (Formula IV). A representative structure is shown below.

In certain embodiments, the β-aminoalkanol is not:

In certain embodiments, the fuel composition does not include:

In certain embodiments, the fuel concentrate does not contain:

In certain embodiments, the beta-aminoalkanol used in the method of reducing low speed pre-ignition events in an engine is not:

In certain embodiments, the low speed pre-ignition (LSPI) reducing additive does not include:

In certain embodiments, the amino alcohol is not:

In certain embodiments, the β-aminoalkanol is or comprises aminoheptylpropanediol, provided that it is not:

In certain embodiments, the fuel composition comprises aminoheptylpropanediol, provided that it is not:

In certain embodiments, the fuel concentrate comprises aminoheptylpropanediol, provided that it is not:

In certain embodiments, the β-aminoalkanol used in the method of reducing low speed pre-ignition events in an engine is or comprises aminoheptylpropanediol, provided that it is not:

In certain embodiments, the low speed pre-ignition (LSPI) reducing additive is or comprises aminoheptylpropanediol, provided that it is not:

In certain embodiments, the amino alcohol is or comprises aminoheptylpropanediol, provided that it is not:

Amino Acids

The fuel additive or lubricating oil additive of the present disclosure can be an aliphatic amino acid, a substituted aliphatic amino acid or a derivative thereof or an acceptable salt thereof. Useful amino acids include amino acids that can be represented by the following general formula:

Wherein R is an "aliphatic" or "aromatic" side chain. Amino acid side chains can be roughly classified as aromatic or aliphatic. Aromatic side chains include aromatic rings. Examples of amino acids with aromatic side chains include, for example, histidine (Formula 2A), phenylalanine (Formula 2B), tyrosine (Formula 2C), tryptophan (Formula 2D), etc. Non-aromatic side chains are roughly classified as "aliphatic", including, for example, alanine (Formula 2E), glycine (Formula 2F), cysteine (Formula 2G), etc.

Amino acids can be natural and/or non-natural α-amino acids. Natural amino acids are amino acids encoded by the genetic code, as well as amino acids 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 mimetics. Analogs are compounds having the same general structure as natural amino acids, except that the R group is not one of the natural amino acids.

Representative examples of natural amino acid analogs include homoserine (Formula 2K), norleucine (Formula 2L), homoproline (Formula 2M) and proline (Formula 2N). Amino acid mimetics are compounds that have a structure that is different from the general chemical structure of an α-amino acid but function in a similar manner to one. Amino acids can be L- or D-amino acids. Representative structures are shown below.

Amino ester

The fuel additive or lubricating oil additive of the present disclosure can be an aminoester, a substituted aminoester or a derivative thereof, or an acceptable salt thereof. The aminoester can be derived from an amino acid (as described above) and an alcohol. Amino acid esters and amino acids can be considered to be derivatives of each other. Useful aminoesters include those that can be represented by the following general formula:

Wherein R is an aliphatic side chain, _R1 is a carbon chain having a length of 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms, in particular methanol or ethanol, preferably methanol.

Aminoesters may include aromatic or aliphatic side chains. Representative examples of aminoesters include alanine methyl ester (Formula 3A), alanine ethyl ester (Formula 3B), glycine methyl ester (Formula 3C) and glycine ethyl ester (Formula 3D). Representative structures are shown below.

2. N＝CX modified additives

The fuel additive or lubricant additive of the present disclosure may have an N=C-X modification, as shown in the following general structure:

Wherein R is H, a monovalent organic group or a monovalent heteroorganic group (described in more detail below), X ₁ and X ₂ are independently H, C, N, O or S, and wherein X ₁ or X ₂ independently includes one or more C ₁ -C ₂₀ alkyl groups (e.g., C ₁ -C ₆ alkyl) or one or more aromatic rings. In some embodiments, X ₁ and X ₂ may include a cyclic structure (e.g., a five-membered, six-membered or seven-membered ring). The cyclic structure may be aromatic or non-aromatic, and varies in the range of fully saturated to fully unsaturated. Suitable examples of additives compatible with Formula 4 include amidines, guanidines, imidazoles, benzamidines, benzimidazoles and aminobenzimidazoles.

Amidine

The fuel additive or lubricating oil additive of the present disclosure can be an amidine, a substituted amidine or a derivative thereof or an acceptable salt thereof. Useful amidines include those that can be represented by the following general formula:

Wherein R ₅ , R ₆ , R ₇ and R ₈ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., including nitrogen, oxygen, sulfur or phosphorus, in the form of a group or moiety bonded by a carbon atom and not containing an acid functional group such as a carboxylic acid or a sulfonic acid) and combinations thereof; and wherein any two or more of R ₅ , R ₆ , R ₇ and R ₈ may optionally be combined 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 varies in the range of fully saturated to fully unsaturated. Organic and heteroorganic groups may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms).

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]-undec-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.

guanidine

The fuel additive or lubricating oil additive of the present disclosure can be guanidine, substituted guanidine or its derivative or its acceptable salt. Useful guanidines include those that can be represented by the following general formula:

Wherein R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group (e.g., including nitrogen, oxygen, sulfur or phosphorus, in the form of a group or part bonded by a carbon atom and not containing an acid functional group such as a carboxylic acid or a sulfonic acid) and combinations thereof; and wherein any two or more of R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ may optionally be combined 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 varies in the range of fully saturated to fully unsaturated. Organic and heteroorganic groups may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms).

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]dodec-5-ene (TBD; Formula 6C), 7-methyl-1,5,7-triazabicyclo[4.4.0]dodec-5-ene (MTBD; Formula 6D) and 1,2-diphenylguanidine (Formula 6I). Representative structures are shown below.

Imidazole

The fuel additive or lubricating oil additive disclosed herein can be imidazole, substituted imidazole or its derivative or its acceptable salt. 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.

3. Triazole additives

The fuel additive or lubricating oil additive of the present disclosure can be triazole, substituted triazole or its derivative or its acceptable salt. Suitable triazole includes 1,2,3-triazole (Formula 8A), 5,6-dimethylbenzotriazole (Formula 8B), 1,2,4-triazole (Formula 8C), piperidine substituted triazole (Formula 8D) and benzotriazole analogs, such as alkyl substituted benzotriazole, such as methyl substituted benzotriazole (Formula 8E). Representative structures are shown below.

4. Benzamidinium Additives

The fuel additive or lubricating oil additive of the present disclosure may be benzamidinium, substituted benzamidinium or derivatives thereof or acceptable salts thereof. Useful benzamidinium additives include those represented by the following general formula 9, wherein R ₁ , R ₂ , and R ₃ are independently C ₁ -C ₂₀ alkyl groups.

Suitable benzamidiniums include N,N-dimethyl-N-octylbenzamidinium-2-oxide (Formula 9A). A representative structure is shown below.

5.Benzoxazole additives

The fuel additive or lubricating oil additive of the present disclosure can be benzoxazole, substituted benzoxazole or its derivative or its acceptable salt. Suitable benzoxazoles include benzoxazole (Formula 10A) and 2-aminobenzoxazole (Formula 10B). Representative structures are shown below.

6. Amine additives

Aromatic amines

The fuel additive or lubricant additive of the present disclosure may be an aromatic amine, a substituted aromatic amine or a derivative thereof or an acceptable salt thereof. The aromatic amine additive may have a general structure as shown in Formula 11-1 or 11-2,

wherein R is independently one or more H or C ₁ -C ₂₀ alkyl, and X is N (eg, RNR) or O ⁻ .

Suitable aromatic amines include 2-methylquinolin-8-amine (Formula 11A). A representative structure is shown below.

Fatty amines

Suitable aliphatic amines are listed below.

Auxiliary additives to reduce LSPI

The following is a description of LSPI reducing co-additives that can be used as fuel or lubricant additives to reduce LSPI activity. Typically, a LSPI reducing co-additive, a substituted LSPI reducing co-additive, or a derivative thereof is used in the form of its salt and in combination with a primary additive to reduce LSPI activity. For example, a β-aminoalkanol (primary additive) and a fatty acid (co-additive) can be combined and used as a LSPI additive. Table 2 lists the co-additive types. Some additives can act as primary additives and/or co-additives.

Table 2

7. Acid additives

fatty acid

Aliphatic acids are non-aromatic carboxylic acids. Suitable aliphatic acids include monocarboxylic acids having the structure

Wherein R is an aliphatic group having 2 to 20 carbon atoms. The aliphatic group may be straight chain or branched and may contain heteroatoms.

Suitable aliphatic acids include 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 ( _C20 ), behenic acid ( _C22 ), 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), 5-methylhexanoic 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-cyclohexylbutanoic acid (Formula 13I) and cyclohexanevaleric acid. Representative structures are shown below.

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.

Alkyl aromatic acid

Suitable alkyl aromatic acids include monocarboxylic acids and dicarboxylic acids. Alkyl carboxylic acids 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 moiety can be optionally substituted with one or more substituents such as hydroxyl, alkoxy and carbonyl (e.g., aldehyde or keto). Suitable examples of alkyl aromatic acids include methyl benzoic acid (Formula 15A) and ethyl benzoic acid (Formula 15B). Representative structures are shown below.

Aromatic acid

Suitable aromatic acids include monocarboxylic acids and dicarboxylic acids. Alkyl carboxylic acids may 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 moiety may optionally be substituted with one or more substituents such as hydroxyl, alkoxy and carbonyl (e.g., aldehyde or keto). Suitable aromatic acids include benzoic acid (Formula 16A), hydroxybenzoic acid (Formula 16B) and tetrahydronaphthoic acid (Formula 16C). Representative structures are shown below.

Hydroxy Acid

Suitable hydroxy acids include those which can be represented by the following general formula:

Where n = 1-3. 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.

Amino Acids

Amino acids can be used as primary and/or secondary additives. Suitable amino acids are as described above.

8. Phenol additives

phenol

Suitable phenols include thymol (Formula 18A), eugenol (Formula 18B), hydroquinone (Formula 18C), resorcinol (Formula 18D), cresol (Formula 18E) and 2-methylquinolin-8-ol (Formula 18G). Representative structures are shown below.

9.1,3 Dicarbonyl Additives

1,3-Diketone

Suitable examples of 1,3-diketone compounds include acetylacetone (Formula 19A) and curcumin (Formula 19B). Representative structures are shown below.

1,3-keto ester

Suitable 1,3-ketoesters are shown below.

10. Hydroxylamide additives

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

wherein _R1 and _R2 are each independently selected from hydrogen or _C1 - _C20 (eg _C3 - _C12 ) alkyl. Suitable hydroxyamides include hydroxymethylacetamide (Formula 21A). A representative structure is shown below.

11. Antioxidants

Suitable antioxidants include monocarboxylic acids and dicarboxylic acids. Alkyl carboxylic acids 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 moiety can be optionally substituted by one or more substituents such as hydroxyl, alkoxy and carbonyl (e.g., aldehyde or keto). Suitable antioxidants include the following.

12. Salicylic acid additives

Salicylic acid

Suitable salicylates include 2-hydroxy-5-(tetracosa-1,3,5,7,9,11,13,15,17,19,21,23-dodecyl-1-yl)benzoic acid-dihydrogen (Formula 23E). Suitable salicylates are shown below.

Salts

The salts of the present disclosure can be prepared in a conventional manner, for example, by mixing a primary additive with a suitable auxiliary additive in an aprotic solvent. The order in which one additive is added to another additive is not important. The primary additive and the auxiliary additive are usually mixed together in an approximately equimolar ratio. Excessive amounts of the primary or auxiliary additive components can be used. For example, the molar ratio of the base to the alkyl carboxylic acid can be about 1.05:1 to 2:1 (e.g., 1.1:1 to 1.5:1). Representative salts are shown below.

Fuel composition

The compounds of the present disclosure may be used as additives in hydrocarbon fuels to prevent or reduce engine knock or pre-ignition events in spark-ignition internal combustion engines.

The concentration of the compounds of the present invention in the hydrocarbon fuel may be from 25 to 5000 parts per million (ppm) by weight (eg, 50 to 1000 ppm).

The compounds of the present disclosure may be formulated into concentrates using inert, stable, oleophilic (i.e., soluble in hydrocarbon fuels) 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, etc., in combination with hydrocarbon solvents, are also suitable for use with the additives of the present invention. In the concentrate, the amount of the additive may be 10 to 70 wt % (e.g., 20 to 40 wt %).

In gasoline fuels, other well-known additives may be used, including oxygenates (e.g., ethanol, methyl tert-butyl ether), other antiknock agents and detergents/dispersants (e.g., hydrocarbyl amines, hydrocarbyl polyoxyalkylene) amines, succinimides, Mannich reaction products, aromatic esters of polyalkylphenoxyalkanols or polyalkylphenoxyaminoalkanes). In addition, friction modifiers, antioxidants, metal deactivators and demulsifiers may be present.

In diesel fuel, other well-known additives may be used, such as pour point depressants, flow improvers, cetane number improvers, and the like.

Fuel soluble, nonvolatile carrier fluids or oils may also be used with the compounds of the present disclosure. A carrier fluid is a chemically inert, hydrocarbon-soluble liquid vehicle that substantially increases the nonvolatile residue (NVR) or solvent-free liquid portion of the fuel additive composition without significantly causing an increase in octane demand. The carrier fluid may be a natural or synthetic oil, such as mineral oil, refined petroleum oil, synthetic polyalkanes and olefins, including hydrogenated and unhydrogenated polyalphaolefins, synthetic polyoxyalkylene derived oils, such as described in U.S. Patents 3,756,793; 4,191,537; 5,004,478; and European Patent Application Publication Nos. 356,726 and 382,159.

The carrier fluid may be used in an amount ranging from 35 to 5000 ppm by weight of the hydrocarbon fuel (e.g., 50 to 3000 ppm of the fuel). When used in a fuel concentrate, the carrier fluid may be present in an amount of 20 to 60 wt % (e.g., 30 to 50 wt %).

Lubricating oil composition

The compounds of the present invention are useful as additives in lubricating oils to prevent or reduce engine knock or pre-ignition events in spark-ignited internal combustion engines.

The concentration of the compound of the present invention in the lubricating oil composition may be 0.01 to 15 wt % (eg, 0.5 to 5 wt %) based on the total weight of the lubricating oil composition.

An oil of lubricating viscosity (sometimes referred to as a "base stock" or "base oil") is the principal liquid component of a lubricant into which additives and possibly other oils are blended, such as to make the final lubricant (or lubricant component). Base oils useful in preparing concentrates and lubricating oil compositions therefrom may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof.

The definitions of base stocks and base oils in this disclosure are the same as those in Annex E of the American Petroleum Institute (API) Publication 1509 ("API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils," December 2016). Group I base stocks have a saturate content of less than 90% and/or a sulfur content greater than 0.03% and 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 stocks have a saturate content of greater than or equal to 90%, a sulfur content of less than or equal to 0.03%, and 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 stocks have a saturate content of greater than or equal to 90%, a sulfur content of less than or equal to 0.03%, and a viscosity index greater than or equal to 120 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.

Natural oils include animal oils, vegetable oils (e.g., castor oil and lard) and mineral oils. Animal and vegetable oils with good thermal oxidation stability can be used. Among natural oils, mineral oils are preferred. The crude oil sources of mineral oils vary greatly, for example, they are paraffins, cycloalkanes or mixed paraffins-cycloalkanes. Oils derived from coal or shale are also useful. The production and purification methods of natural oils are also different, for example, their distillation range and whether they are straight run or cracking, hydrofining or solvent extraction.

Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized and copolymerized olefins (e.g., polybutene, polypropylene, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alpha-olefin copolymers). Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oils. For example, PAOs derived from _C8 to _C14 olefins, such as _C8 , _C10 , _C12 , _C14 olefins, or mixtures thereof, can be used.

Other useful fluids for use as base oils include unconventional base oils that have been processed, preferably catalytically or synthetically, to provide high performance characteristics.

Unconventional base stocks/base oils include one or more base oil blends derived from one or more gas-to-liquid (GTL) materials as well as isomerized/isomerized dewaxed base oils derived from natural waxes or waxy feeds, mineral and/or non-mineral oil waxy feeds (e.g., slack wax, natural waxes) and waxy feedstocks such as gas oils, waxy fuel hydrocracking bottoms, waxy raffinates, hydrocrackates, thermal crackers or other minerals, mineral oils and even non-petroleum derived waxy materials such as those obtained from coal liquefaction or shale oil, and mixtures of these base stocks.

The base oil used in the lubricating oil composition of the present disclosure is any of various oils corresponding to API Group I, Group II, Group III, Group IV and Group V, and mixtures thereof, preferably API Group II, III, IV, V oils, and mixtures thereof, and Group III to V base oils are more preferred due to their excellent volatility, stability, viscosity and cleanliness characteristics.

Typically, the base oil has a kinematic viscosity at 100° C. (ASTM D445) of 2.5 to 20 mm ² /s (eg, 3 to 12 mm ² /s, 4 to 10 mm ² /s, or 4.5 to 8 mm ² /s).

The lubricating oil composition of the present invention may also contain conventional lubricant additives to impart 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 mixed with antioxidants, ashless dispersants, antiwear agents, detergents such as metal detergents, rust inhibitors, demisters, demulsifiers, friction modifiers, metal deactivators, pour point depressants, viscosity improvers, defoamers, cosolvents, packaging extenders, corrosion inhibitors, dyes, extreme pressure agents, etc. and mixtures thereof. Various additives are known and commercially available. These additives or their analogous compounds may be used to prepare the lubricating oil composition of the present invention by conventional mixing methods.

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 the ashless dispersant will be an amount sufficient to impart the desired dispersibility to the lubricant. Typically, unless otherwise specified, the concentration of each of these additives may be in the range of about 0.001 to about 20 weight percent, such as about 0.01 to about 10 weight percent.

Example

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

Embodiment 1-45

The test compounds were blended into gasoline or lubricating oil and their ability to reduce LSPI events was determined using the test method described below.

The LSPI test was conducted using a GM 2.0L LHU 4-cylinder gasoline turbocharged direct injection engine. Each cylinder was equipped with a combustion pressure sensor.

A six-segment test procedure is used to determine the number of LSPI events that occur at an engine speed of 2000 rpm and a load of 275 Nm. The LSPI test condition is run for 28 minutes with an idle interval between each segment. The first segment is used for oil conditioning and does not count the number of LSPI events. Each segment is truncated slightly to eliminate the transient portion. Each truncated segment typically has approximately 100,000 combustion cycles (25,000 combustion cycles per cylinder). In total, the five truncated segments count for approximately 500,000 combustion cycles (125,000 combustion cycles per cylinder) for LSPI events. If the engine is unable to complete all six segments, the test may be shortened.

LSPI-affected combustion cycles are determined by monitoring peak cylinder pressure (PP) and crank angle at 5% total heat release (AI5). LSPI-affected combustion cycles are defined as (1) PP greater than five standard deviations from the mean PP for a given cylinder and truncated segment, and (2) AI5 greater than five standard deviations from the mean for a given cylinder and truncated segment.

The LSPI frequency is reported as the number of combustion cycles affected by LSPI per million combustion cycles and is calculated as follows:

LSPI frequency = [(total number of combustion cycles affected by LSPI in five truncated segments)/(total number of combustion cycles in five truncated segments)] × 1,000,000

Additives associated with test fuels and/or test lubricants that reduce LSPI frequency when compared to a corresponding baseline fuel and/or baseline lubricant are considered LSPI frequency mitigating additives. The test results are listed in Table 2.

Claims (13)

1. A fuel composition comprising: (1) greater than 50% by weight of a hydrocarbon fuel having a boiling point in the gasoline or diesel range, and (2) a small amount of an additive that reduces low speed pre-ignition LSPI, said additive comprising amidine or One or more of β-aminoalkanols or their salts having the following structure: wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, aromatic rings and C ₁ -C ₂₀ alkyl groups, and R ₅ is hydrogen or an alcohol having the structure –(CH)R ₆ -OH, where R ₆ is hydrogen, C ₁ -C ₁₀ alkyl, or C ₁ -C ₁₀ alkenyl. 2. The fuel composition of claim 1, wherein two or more of _R1 , _R2 , _R3 and _R4 form a ring structure. 3. The fuel composition of claim 1, wherein at least one of _R1 , _R2 , _R3 and _R4 is an aromatic ring. 4. The fuel composition of claim 1, wherein the low speed pre-ignition LSPI reducing additive is aminoheptylpropanediol, aminooctylpropanediol or aminododecylethanol. 5. The fuel composition according to claim 1, further comprising an auxiliary additive for reducing low speed pre-ignition LSPI, 2-methylquinoline-8-oleate or C24-salicylate. 6. The fuel composition according to claim 1, further comprising an auxiliary additive for reducing low speed pre-ignition LSPI, the auxiliary additive comprising one or more of the following: acid additive, phenol additive, 1,3-dicarbonyl additive , isohydroxyamide additives, antioxidant additives or salicylic acid additives. 7. A fuel concentrate comprising: (1) 90 to 30% by weight of an organic solvent having a boiling point between 65°C and 205°C, and (2) 10 to 70% by weight of an additive component that reduces low speed pre-ignition LSPI , the additive component includes one or more of amidine or β-aminoalkanol having the following structure or their salts: wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, aromatic rings and C ₁ -C ₂₀ alkyl groups, and R ₅ is hydrogen or an alcohol having the structure –(CH)R ₆ -OH, where R ₆ is hydrogen, C ₁ -C ₁₀ alkyl, or C ₁ -C ₁₀ alkenyl. 8. The fuel concentrate of claim 7, wherein two or more of _R1 , _R2 , _R3 and _R4 form a ring structure. 9. The fuel concentrate of claim 7, wherein at least one of _R1 , _R2 , _R3 and _R4 is an aromatic ring. 10. The fuel concentrate of claim 7, wherein the low speed pre-ignition LSPI reducing additive is aminoheptylpropanediol, aminooctylpropanediol or aminododecylethanol. 11. The fuel concentrate of claim 7, further comprising an auxiliary additive to reduce low speed pre-ignition LSPI, 2-methylquinoline-8-oleate or C24-salicylate. 12. A method of reducing low speed pre-ignition events in an engine, the method comprising providing to the engine a fuel composition comprising: (1) greater than 50% by weight of a hydrocarbon fuel having a boiling point in the gasoline or diesel range and (2) a small amount of additives that reduce low-speed pre-ignition LSPI, the additives containing one or more of amidine or β-aminoalkanol having the following structure or their salts: wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen and C ₁ -C ₂₀ alkyl, and R ₅ is hydrogen or an alcohol having the structure –(CH)R ₆ -OH, where R ₆ is Hydrogen, C ₁ -C ₁₀ alkyl, or C ₁ -C ₁₀ alkenyl. 13. The method of claim 12, wherein the additive that reduces low speed pre-ignition LSPI is aminoheptylpropanediol, aminooctylpropanediol or aminododecylethanol.