JP2021518470A - Spark Ignition Compositions and Methods for Preventing or Reducing Slow Pre-Ignition of Internal Combustion Engines - Google Patents

Abstract

(I) Amino Additive, (ii) Amin Additive, (iii) Triazole Additive, (iv) Benz Amidinium Additive, (v) Benzoxazole Additive, or (vi) N = CX Motif Addition Fuel and lubricant compositions are provided that include a primary slow pre-ignition (LSPI) reduction additive containing an agent. Methods for using these compositions to prevent or reduce slow pre-ignition events in spark ignition engines are also provided.

Description

Technical Fields The present disclosure relates to fuel and lubricant compositions for spark ignition engines, and methods for using them to prevent or reduce slow pre-ignition events.

Background Turbocharged or supercharged engines (ie, boosted internal combustion engines) may exhibit anomalous combustion phenomena known as stochastic pre-ignition or slow pre-ignition (or "LSPI"). LSPI is an event that can include very high pressure spikes, premature combustion at improper crank angles, and knocks. All of these, individually or in combination, can cause engine deterioration and serious damage. However, since LSPI events occur only in sporadic and uncontrolled manners, it is difficult to identify the cause of this phenomenon and develop solutions to suppress it.

Pre-ignition is a form of combustion that results in the ignition of the air-fuel mixture (air-fuel mixture) in the combustion chamber prior to the desired ignition by the igniter. Pre-ignition is usually a problem during heavy-duty engine operation, as heat from engine operation can heat parts of the combustion chamber to a temperature sufficient to ignite the air-fuel mixture on contact. Become. This type of pre-ignition is sometimes referred to as hotspot pre-ignition.

More recently, intermittent abnormal combustion has been observed in low speed and medium to high load boosted internal combustion engines. For example, low speed pre-ignition (LSPI) may occur randomly and stochastically during operation of an engine with an mean effective pressure (BMEP) of the brakes of 10 bar or more under load at 3000 rpm or less. The compression stroke time is the longest during low-speed engine operation.

Previous studies have shown that turbocharger use, engine design, engine coating, piston geometry, fuel selection, and / or engine oil additives may contribute to an increase in LSPI events. Therefore, effective fuel and engine oil additive components and / or combinations are needed to reduce or eliminate LSPI.

ここで、Ｘ_１およびＸ２は独立してＨ、Ｃ、Ｎ、Ｏ、またはＳであり；ここで、Ｘ_１またはＸ_２は、独立して、１つまたは複数のＣ_１〜Ｃ_２０アルキル基または１つまたは複数の芳香族基を含む。 Overview In one aspect, (1) more than 50% by weight hydrocarbon fuel boiling in the gasoline or diesel range, and (2) a small amount of one or more primary slow pre-ignition (LSPI) reducing additives, including: Fuel compositions comprising: (i) amino additive, (ii) amine additive, (iii) triazole additive, (iv) benzamidinium additive, (v) benzoxazole additive, or (v) vi) N = CX motif additive having the following structure

Here, X ₁ and X 2 are independently H, C, N, O, or S; where X ₁ or X ₂ is independently one or more C _1- C ₂₀ alkyl groups. Or it contains one or more aromatic groups.

ここで、Ｘ_１およびＸ_２は独立してＨ、Ｃ、Ｎ、Ｏ、またはＳであり；ここで、Ｘ_１またはＸ_２は、独立して、１つまたは複数のＣ_１〜Ｃ_２０アルキル基または１つまたは複数の芳香族基を含む。 In another embodiment, (1) 90 to 30% by weight organic solvent boiling in the range of 65 ° C. to 205 ° C., and (2) 10 to 70% by weight additive component selected from one or more of the following: Fuel concentrates containing, are provided: (i) amino additives, (ii) amine additives, (iii) triazole additives, (iv) benzamidinium additives, (v) benzoxazole additives, Or (vi) N = CX motif additive having the following structure

Here, X ₁ and X ₂ are independently H, C, N, O, or S; where X ₁ or X ₂ is independently one or more C _{1 to} C ₂₀ alkyl. Includes groups or one or more aromatic groups.

ここで、Ｘ_１およびＸ_２は、独立して、Ｈ、Ｃ、Ｎ、Ｏ、またはＳであり；Ｘ_１またはＸ_２は、独立して、１つまたは複数のＣ_１−Ｃ_２０アルキル基または１つまたは複数の芳香族基を含む。 In a further embodiment, 0.01-15% by weight of the component selected from (1) more than 50% by weight of base oil and (2) one or more Primary Slow Pre-Ignition (LSPI) Reduction Additives including: Lubricating oil compositions comprising, are provided: (i) amino additives, (ii) amine additives, (iii) triazole additives, (iv) benzamidinium additives, (v) benzoxazole additives. , Or (vi) N = CX motif additive having the following structure

Here, X ₁ and X ₂ are independently H, C, N, O, or S; X ₁ or X ₂ are independently one or more C _1- C ₂₀ alkyl groups. Or it contains one or more aromatic groups.

Detailed explanation
Introduction In the present specification, the following words and expressions have the meanings that belong to the following when and when used.

"Gasoline" or "gasoline boiling component" refers to a composition comprising at least predominantly C ₄ -C ₁₂ hydrocarbons. In one embodiment, the boiling range components of gasoline or gasoline, at least predominantly comprises _C 4 _{-C 12} hydrocarbons, boiling range of about an additional 100 ° F (37.8 ℃) from about 400 ° F (204 ℃) Is further defined to refer to a composition having. Boiling range components of alternative embodiments, gasoline or gasoline, about 100 ° F (37.8 ℃) having a boiling range of about 400 ° F (204 ℃), at least predominantly _C 4 _{-C 12} hydrocarbon It is defined to refer to a composition comprising ASTMD4814 and is further defined to satisfy ASTMD4814.

The term "diesel" refers to intermediate fraction fuels containing _{at least mainly C 10-} C _{25 hydrocarbons.} In one embodiment, the diesel comprises at least mainly C _10- C ₂₅ hydrocarbons and further has a boiling range of about 165.6 ° C (330 ° F) to about 371.1 ° C (700 ° F). Further defined to point to. In an alternative embodiment, the diesel contains at least mainly C _10- C ₂₅ hydrocarbons and has a boiling range of about 165.6 ° C (330 ° F) to about 371.1 ° C (700 ° F). Further defined to satisfy the ASTMD975.

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

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

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

By "small amount" is meant less than 50% by weight of the composition as expressed with respect to the stated additives and with respect to the total weight of the composition considered to be the active ingredient of the additive.

An "analog" is similar to other compounds, but differs with respect to certain components such as one or more atoms, functional groups, substructures replaced by other atoms, groups, or substructures. It is a compound having a structure.

A "homlogue" is a compound that belongs to a series of compounds with different repeating units. Alkanes are an example of homologues. For example, ethane and propane are homologues because they differ only in the length _{of the repeating unit (-CH 2-).} Homologues can be considered as certain types of analogs.

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

An "engine" or "combustion engine" is a heat engine in which the combustion of fuel occurs in the combustion chamber. An "internal combustion engine" is a heat engine that generates fuel in a limited space ("combustion chamber"). A "spark ignition engine" is a heat engine whose combustion is usually ignited by sparks from a spark plug. This is in contrast to "compressive ignition engines," usually diesel engines. In this engine, the heat generated by compression and fuel injection is sufficient to initiate combustion without external sparks.

Low speed pre-ignition (LSPI)
Low speed pre-ignition (LSPI) is a direct injection that produces during operation a brake mean effective pressure level in excess of 1000 kPa (10 bar) at an engine speed of 1500-2500 rpm (rpm), such as an engine speed of 1500-2000 rpm. Boost (turbocharged or supercharged), spark ignition (gasoline) Most likely or more likely to occur in internal combustion engines. "Brake mean effective pressure" (BMEP) is defined as the work accomplished during the engine cycle divided by the engine displacement, and the engine torque is normalized by the engine displacement. The word "brake" refers to the actual torque or output available on the engine flywheel as measured by the motor. Therefore, BMEP is a measure of engine effective energy output.

The fuel or lubricating oil compositions 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, minimize or prevent engine knocking and preignition problems. It was found to do.

Primary LSPI Reducing Additives The following is a description of primary additives that can be used as fuel or lubricant additives to reduce LSPI activity. The primary LSPI reducing additive can be used as a single additive and / or with other primary additives and / or with one or more secondary LSPI reducing additives (discussed below). If more than one additive is used, the additive may be in the form of a salt. Furthermore, when two or more additives are used, there can be a synergistic effect between the two or more additives. In general, these additives are soluble in fuel or oil at the concentrations required to achieve the desired LSPI reduction levels. Table 1 summarizes the types of primary additives.

ここで、Ｒ_１、Ｒ_２、Ｒ_３、およびＲ_４は、それぞれ、水素およびＣ_１〜Ｃ_２０アルキル（例えば、Ｃ_１〜Ｃ_６アルキル）基から独立して選択される。そして、２つ以上のＲ_１、Ｒ_２、Ｒ_３、およびＲ_４は、場合により一緒に結合して、環構造を形成することができる（例えば、５員、６員、または７員環）。いくつかの実施形態において、Ｒ_１、Ｒ_２、Ｒ_３、およびＲ_４は、独立して、１つ以上の芳香環を含み得る。 1. 1. Amino additive
β-Amino Alkanol The fuel additive or lubricating oil additive of the present disclosure can be β-aminoalkanol, substituted β-aminoalkanol, derivatives thereof or acceptable salts thereof. Useful β-aminoalkanols include those that can be expressed by the following general formula.

Here, R ₁ , R ₂ , R ₃ , and R ₄ are selected independently of hydrogen and C _{1 to} C ₂₀ alkyl (eg, C _{1 to} C _{6 alkyl) groups, respectively.} Then, two or more R ₁ , R ₂ , R ₃ , and R ₄ can optionally be combined together to form a ring structure (eg, a 5-membered, 6-membered, or 7-membered ring). .. In some embodiments, R ₁ , R ₂ , R ₃ , and R ₄ may independently contain one or more aromatic rings.

β-Aminoalkanol contains at least 2 carbon atoms (eg, 4 to 30 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, 5 to 30). It has 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), cycloleucinol (formula 1M), cyclohexyl amine Ricinol (Formula 1N), Prolinol (Formula 1O), 2- (Hydroxymethyl) piperidine (Formula 1P), 2-Aminocyclopentanol (Formula 1Q), and 2-Aminocyclohexanol (Formula 1R). A typical structure is shown below.

ここで、Ｒは「脂肪族」または「芳香族」側鎖である。アミノ酸側鎖は、芳香族または脂肪族に大別できる。芳香族側鎖は芳香環を含む。芳香族側鎖を有するアミノ酸の例には、例えば、ヒスチジン（式２Ａ）、フェニルアラニン（式２Ｂ）、チロシン（式２Ｃ）、トリプトファン（式２Ｄ）などが含まれる。非芳香族側鎖は、「脂肪族」として大まかに分類され、例えば、アラニン（式２Ｅ）、グリシン（式２Ｆ）、システイン（式２Ｇ）などを含む。 Amino Acids The fuel additives or lubricating oil additives of the present disclosure can be aliphatic amino acids, substituted aliphatic amino acids, or derivatives thereof, or acceptable salts thereof. Useful amino acids include amino acids that can be represented by the following general formula:

Here, R is an "aliphatic" or "aromatic" side chain. Amino acid side chains can be broadly classified into aromatics and aliphatics. The aromatic side chain contains an aromatic ring. Examples of amino acids having an aromatic side chain include, for example, histidine (formula 2A), phenylalanine (formula 2B), tyrosine (formula 2C), tryptophan (formula 2D) and the like. Non-aromatic side chains are broadly classified as "aliphatic" and include, for example, alanine (formula 2E), glycine (formula 2F), cysteine (formula 2G) and the like.

Amino acids can be natural and / or non-natural α-amino acids. Natural amino acids are amino acids encoded by the genetic code and amino acids derived from them. These include, for example, hydroxyproline (formula 2H), γ-carboxyglutamic acid (formula 2I), and citrulline (formula 2J). As used herein, the term "amino acid" also includes amino acid analogs and mimetics. Analogs are compounds that have the same general structure as natural amino acids, except that the R group is not found in natural amino acids.

Representative examples of naturally occurring 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 different from the general chemical structure of α-amino acids, but function in the same way. The amino acid can be an L- or D-amino acid. A typical structure is shown below.

ここで、Ｒは脂肪族側鎖であり、Ｒ_１は長さが１から２０個の炭素原子、好ましくは１から４個の炭素原子、特にメタノールまたはエタノール、好ましくはメタノールである炭素鎖である。 Amino Esters The fuel additives or lubricating oil additives of the present disclosure can be amino esters, substituted amino esters, or derivatives thereof, or acceptable salts thereof. Amino esters can be derived from amino acids (as described above) and alcohols. Amino esters and amino acids can be considered derivatives of each other. Useful amino esters include those that can be expressed by the following general formula.

Here, R is an aliphatic side chain, and R ₁ is a carbon atom having a length of 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms, particularly methanol or ethanol, preferably methanol. ..

Amino esters may include aromatic or aliphatic side chains. Representative examples of aminoesters include methyl alanate (formula 3A), ethyl alanate (formula 3B), methyl glycine (formula 3C), and ethyl glycine (formula 3D). A typical structure is shown below.

ここで、ＲはＨ、一価有機基、または一価ヘテロ有機基（以下でより詳細に説明する）であり、Ｘ_１およびＸ_２は独立してＨ、Ｃ、Ｎ、Ｏ、またはＳであり、Ｘ_１またはＸ_２は独立して１つまたは複数のＣ_１−Ｃ_２０アルキル基（例えば、Ｃ_１−Ｃ_６アルキル）または１つまたは複数の芳香環を含む。いくつかの実施形態では、Ｘ_１およびＸ_２は、環状構造（例えば、５員、６員、または７員環）を含み得る。環状構造は、芳香族または非芳香族であり得、ならびに完全に飽和しているものから完全に不飽和のものまで変化し得る。式４と適合性のある添加剤の適切な例には、アミジン、グアニジン、イミダゾール、ベンズアミジン、ベンズイミダゾール、およびアミノベンズイミダゾールが含まれる。 2. N = CX Motif Additives The fuel or lubricating oil additives of the present disclosure may have an N = CX motif as shown in the generalized structure below.

Here, R is H, a monovalent organic group, or a monovalent heteroorganic group (described in more detail below), and X ₁ and X ₂ are independently H, C, N, O, or S. Yes, X ₁ or X ₂ independently comprises one or more C _1- C ₂₀ alkyl groups (eg, C _1- C ₆ alkyl) or one or more aromatic rings. In some embodiments, X ₁ and X ₂ may include an annular structure (eg, a 5-membered, 6-membered, or 7-membered ring). The cyclic structure can be aromatic or non-aromatic, and can vary from fully saturated to completely unsaturated. Suitable examples of additives compatible with Formula 4 include amidine, guanidine, imidazole, benzamidine, benzimidazole, and aminobenzimidazole.

ここで、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８はそれぞれ、水素、一価有機基、一価ヘテロ有機基（例えば、炭素原子を介して結合するがカルボン酸やスルホン酸などの酸官能基を含まない基または部分の形態の窒素、酸素、硫黄またはリンを含む）、およびそれらの組み合わせから独立して選択される。そして、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８のうちの任意の２つ以上が場合により一緒に結合して、環状構造（例えば、５員、６員、または７員環）を形成することができる。環状構造は、芳香族または非芳香族であり得、ならびに完全に飽和しているものから完全に不飽和のものまで変化し得る。有機基およびヘテロ有機基は、１から１０個の炭素原子（例えば、１から６個の炭素原子）を有し得る。 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 expressed by the following general formula:

Here, R ₅ , R ₆ , R ₇ and R ₈ are hydrogen, monovalent organic group and monovalent heteroorganic group (for example, acid functional groups such as carboxylic acid and sulfonic acid which are bonded via carbon atoms, respectively. (Contains nitrogen, oxygen, sulfur or phosphorus) in the form of groups or moieties that do not contain, and combinations thereof are selected independently. Then, _{any two or more of R 5} , R ₆ , R ₇ and R ₈ may optionally be combined together to form a cyclic structure (eg, a 5-membered, 6-membered, or 7-membered ring). Can be done. The cyclic structure can be aromatic or non-aromatic, and can vary from fully saturated to completely unsaturated. Organic and heteroorganic groups can have 1 to 10 carbon atoms (eg, 1 to 6 carbon atoms).

Representative examples of suitable amidines are 1,4,5,6-tetrahydropyrimidines (formula 5A), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidines (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) are included. A typical structure is shown below.

ここで、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２およびＲ_１３はそれぞれ、水素、一価有機基、一価ヘテロ有機基（例えば、炭素原子を介して結合するがカルボン酸やスルホン酸などの酸官能基を含まない基または部分の形態の窒素、酸素、硫黄またはリンを含む）およびそれらの組み合わせから独立して選択される。そして、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２およびＲ_１３のうちの任意の２つ以上が、場合により一緒に結合して、環状構造（例えば、５員、６員、または７員環）を形成することができる。環状構造は、芳香族または非芳香族であり得、ならびに完全に飽和しているものから完全に不飽和のものまで変化し得る。有機基およびヘテロ有機基は、１から１０個の炭素原子（例えば、１から６個の炭素原子）を有し得る。 Guanidine The fuel additive or lubricating oil additive of the present disclosure can be guanidine, substituted guanidine, or derivatives thereof, or acceptable salts thereof. Useful guanidines include those that can be expressed by the following general formula:

Here, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen, monovalent organic group and monovalent heteroorganic group (for example, carboxylic acid and sulfonic acid which are bonded via carbon atoms, respectively). It is independently selected from (containing nitrogen, oxygen, sulfur or phosphorus) in the form of groups or moieties free of acid functional groups and combinations thereof. Then, _{any two or more of R 9} , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ may optionally be joined together to form a cyclic structure (eg, a 5-membered, 6-membered, or 7-membered ring). Can be formed. The cyclic structure can be aromatic or non-aromatic, and can vary from fully saturated to completely unsaturated. Organic and heteroorganic groups can have 1 to 10 carbon atoms (eg, 1 to 6 carbon atoms).

Representative examples of suitable guanidines are 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] dessie-5-ene (TBD; formula 6C), 7-methyl-1,5,7-triazabicyclo [4.4. 0] Dessie-5-ene (MTBD; formula 6D) and 1,2-diphenylguanidine (formula 6I) are included. A typical structure is shown below.

Imidazole The fuel additive or lubricating oil additive of the present disclosure can be an imidazole, a substituted imidazole, or a derivative thereof, or an acceptable salt thereof. Suitable imidazoles include imidazole (formula 7A), 1-methylimidazole (formula 7B), 1-ethylimidazole (formula 7D), 1-propyl imidazole (formula 7E), 1-n-butyl imidazole (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) are included. A typical structure is shown below.

3. 3. Triazole Additives The fuel additives or lubricating oil additives of the present disclosure can be triazoles, substituted triazoles, or derivatives thereof, or acceptable salts thereof. Suitable triazoles include 1,2,3-triazole (formula 8A), 5,6-dimethylbenzotriazole (formula 8B), and 1,2,4-triazole (formula 8C). A typical structure is shown below.

4. Benz Amidinium Additives The fuel additives or lubricating oil additives of the present disclosure can be benz amidinium, substituted benz amidinium, or derivatives thereof, or acceptable salts thereof. Useful benzamidinium additives include those that can be represented by the following general formula 9, where R ₁ , R ₂ , and R ₃ are independently C _{1 to} C ₂₀ alkyl groups. Is.

Suitable benzamidiniums include N, N-dimethyl-N-octylbenzamidium-2-oxide (formula 9A). A typical structure is shown below.

5. Benzoxazole Additives The fuel additives or lubricating oil additives of the present disclosure can be benzoxazoles, substituted benzoxazoles, or derivatives thereof, or acceptable salts thereof. Suitable benzoxazoles include benzoxazoles (formula 10A) and 2-aminobenzoxazoles (formula 10B). A typical structure is shown below.

ここで、Ｒは独立して１つ以上のＨまたはＣ_１−Ｃ_２０アルキル基であり、ＸはＮ（例えば、Ｒ−Ｎ−Ｒ）またはＯである。 6. Amine additive
Aromatic Amines The fuel additives or lubricating oil additives of the present disclosure can be aromatic amines, substituted aromatic amines, or derivatives thereof, or acceptable salts thereof. The aromatic amine additive can have a generalized structure represented by formula 11-1 or 11-2.

Here, R is independently one or more H or C _1- C ₂₀ alkyl groups, and X is N (eg, RN-R) or O.

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

Aliphatic amines Suitable aliphatic amines are shown below.

Secondary LSPI Reducing Additives The following is a description of secondary LSPI reducing additives that can be used as fuel or lubricating additives to reduce LSPI activity. Generally, secondary LSPI reducing additives, substituted secondary LSPI reducing additives, or derivatives thereof are used in combination with primary additives in the form of salts thereof to reduce LSPI activity. For example, β-aminoalkanol (primary additive) and aliphatic acid (secondary additive) can be combined and used as an LSPI additive. Table 2 shows the types of secondary additives. Some additives can function as primary and / or secondary additives.

ここで、Ｒは、２から２０個の炭素原子を有する脂肪族基である。脂肪族基は、線状または分枝状であり得、ヘテロ原子を含み得る。 7. Acid additive
Aliphatic Acids Aliphatic acids are non-aromatic carboxylic acids. Suitable fatty acids include monocarboxylic acids having the following structure:

Here, R is an aliphatic group having 2 to 20 carbon atoms. Aliphatic groups can be linear or branched and can contain heteroatoms.

Suitable fatty acids include: hexanic acid (formula 13A), heptanic acid (formula 13B), octanoic acid (formula 13C), nonanoic acid (formula 13D), decanoic acid (formula 13E), undecanoic acid. , Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid (C ₂₀ ), behenic acid (C ₂₂ ), 2-ethylbutyric acid (formula 13F), 3,3-dimethylbutyric acid, 2-methylpentanoic acid (C) ₆ ), 2-methylhexanoic acid (C ₇ ), 4-methylhexanoic acid (C ₇ ), 5-methylhexanoic acid (C ₇ ), 2,2-dimethylpentanoic acid (C ₇ ), 2-propylpentanoic acid (C ₈ ), 2-ethylhexanoic acid (formula 13G), 2-methylheptanic acid (C ₈ ), isooctanoic acid (C ₈ ), 3,5,5-trimethylhexanoic acid (C ₉ ), 4-methyloctane Acid (C ₉ ), 4-methylnonanoic acid, (C ₁₀ ), isodecanoic acid (C ₁₀ ), 2-butyloctanoic acid (C ₁₂ ), isotridecanoic acid (C ₁₃ ), 2- _{hexyl decanoic acid (C 16} ), iso Palmitic acid (C ₁₆ ), isostearic acid (formula 13H), 3-cyclohexylpropionic acid, 4-cyclohexylbutyric acid (formula 13I), and cyclohexanepentanoic acid. A typical structure is shown below.

Unsaturated Acids Suitable unsaturated acids include any organic acid containing double or triple carbon-carbon bonds. Representative unsaturated acids include unsaturated fatty acids such as maleic acid (formula 14A), fumaric acid (formula 14B), and palmitoleic acid (formula 14C) and oleic acid (formula 14D). A typical structure is shown below.

Alkyl Aromatic Acids Suitable alkyl aromatic acids include both monocarboxylic acids and dicarboxylic acids. Alkylcarboxylic acids are 6 or more carbon atoms (eg, 6 to 24 carbon atoms, 6 to 20 carbon atoms, 8 to 24 carbon atoms, 8 to 20 carbon atoms, or 8 to 18 carbon atoms. Can have (1) carbon atoms). The alkyl moiety can optionally be substituted with one or more substituents such as hydroxy, alkoxy and carbonyl (eg, aldehyde or ketone) groups. Suitable examples of alkyl aromatic acids include methyl benzoic acid (formula 15A) and ethyl benzoic acid (formula 15B). A typical structure is shown below.

Aromatic Acids Suitable aromatic acids include both monocarboxylic acids and dicarboxylic acids. Alkylcarboxylic acids are 6 or more carbon atoms (eg, 6 to 24 carbon atoms, 6 to 20 carbon atoms, 8 to 24 carbon atoms, 8 to 20 carbon atoms, or 8 to 18 carbon atoms. Can have (1) carbon atoms). The alkyl moiety can optionally be substituted with one or more substituents such as hydroxy, alkoxy and carbonyl (eg, aldehyde or ketone) groups. Suitable aromatic acids include benzoic acid (formula 16A), hydroxybenzoic acid (formula 16B), and tetralincarboxylic acid (formula 16C). A typical structure is shown below.

ここで、ｎ＝１から３である。ヒドロキシ酸の適切な例には、グリコール酸（式１７Ａ）、乳酸（式１７Ｂ）、リンゴ酸（式１７Ｃ）、酒石酸（式１７Ｄ）、およびクエン酸（式１７Ｅ）が含まれる。代表的な構造を以下に示す。

Hydroxy Acids Suitable hydroxy acids include those that can be represented by the following general formulas.

Here, n = 1 to 3. Suitable examples of hydroxy acids include glycolic acid (formula 17A), lactic acid (formula 17B), malic acid (formula 17C), tartaric acid (formula 17D), and citric acid (formula 17E). A typical structure is shown below.

Amino Acids Amino acids can be used as primary and / or secondary additives. Suitable amino acids have been previously described above.

8. Phenol additive
Phenols Suitable phenols include thymol (formula 18A), eugenol (formula 18B), hydroquinone (formula 18C), resorcinol (formula 18D), cresol (formula 18E) and 2-methylquinoline-8-ol (formula 18G). included. A typical structure is shown below.

9.1,3 dicarbonyl additive
Suitable examples of the 1,3 diketone 1,3 diketone compounds include acetylacetone (formula 19A), and curcumin (formula 19B). A typical structure is shown below.

1,3 ketoesters Suitable 1,3 ketoesters are shown below.

ここで、Ｒ_１およびＲ_２は、それぞれ、水素またはＣ_１−Ｃ_２０（例えば、Ｃ_３−Ｃ_１２）アルキル基から独立して選択される。適切なヒドロキサミドには、ヒドロキシメチルアセトアミド（式２１Ａ）が含まれる。代表的な構造を以下に示す。

10. Hydroxamide Acid Additive Hydroxamide is a hydroxy derivative of the amide. Useful hydroxamides include those that can be expressed by the following general formula:

Here, R ₁ and R ₂ are selected independently of hydrogen or a C _1- C ₂₀ (eg, C _3- C _{12) alkyl group, respectively.} Suitable hydroxamides include hydroxymethylacetamide (formula 21A). A typical structure is shown below.

11. Antioxidants Additives Suitable antioxidants include both monocarboxylic acids and dicarboxylic acids. Alkylcarboxylic acids are 6 or more carbon atoms (eg, 6 to 24 carbon atoms, 6 to 20 carbon atoms, 8 to 24 carbon atoms, 8 to 20 carbon atoms, or 8 to 18 carbon atoms. Can have (1) carbon atoms). The alkyl moiety can optionally be substituted with one or more substituents such as hydroxy, alkoxy and carbonyl (eg, aldehyde or ketone) groups. Suitable antioxidants include:

12. Salicylate additive
Salicylate Suitable salicylate, 2-hydroxy-5- (tetracosa -1,3,5,7,9,11,13,15,17,19,21,23- Dodekain-1-yl) benzoic acid - Two Hydrogen (formula 23E) is included. Appropriate salicylates are shown below.

Salts of salt present disclosure, by conventional means, for example, in an aprotic solvent can be prepared by mixing the primary and additives appropriate secondary additives. The order in which one additive is added to the other is not important. The primary and secondary additives are usually mixed in approximately equimolar ratios. Excessive primary or secondary additive components can be used. For example, the molar ratio of base to alkylcarboxylic acid can be from about 1.05: 1 to 2: 1 (eg, 1.1: 1 to 1.5: 1). Typical salts are shown below.

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

Concentrations of the compounds of the present disclosure in hydrocarbon fuels can range from 25 to 5000 parts per million (ppm) by weight (eg, 50 to 1000 ppm).

The compounds of the present disclosure can be formulated as concentrates using an inert, stable lipophilic (ie, soluble in hydrocarbon fuels) organic solvent that boils in the range of 65 ° C to 205 ° C. Aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene, or high boiling aromatic or aromatic thinners can be used. It is also suitable for use in combination with the present additive in an aliphatic alcohol containing 2 to 8 carbon atoms such as ethanol, isopropanol, methylisobutylcarbinol and n-butanol in combination with a hydrocarbon solvent. In the concentrate, the amount of additive can range from 10 to 70% by weight (eg, 20 to 40% by weight).

For gasoline fuels, oxygenated products (eg ethanol, methyl tert-butyl ether), other antiknock agents, and cleaning agents / dispersants (eg hydrocarbylamines, hydrocarbylpoly (oxyalkylene) amines, succinimides, Mannig reaction products, etc. Other well-known additives can be used, including aromatic esters of polyalkylphenoxyalkanol, or polyalkylphenoxyaminoalkanols). In addition, friction modifiers, antioxidants, metal inactivating agents and demulsifying agents may be present.

For diesel fuel, other well-known additives such as pour point depressants, flow improvers, and cetane improvers can be used.

Fuel-soluble non-volatile carrier fluids or oils can also be used with the compounds of the present disclosure. The carrier fluid is a chemically inert hydrocarbon-soluble liquid vehicle that does not overwhelmingly contribute to the increase in octane requirements, while being solvent-free of non-volatile residues (NVR) or fuel additive compositions. Substantially increases the liquid fraction. Carrier fluids may be natural or synthetic oils such as mineral oils, refined petroleum oils, synthetic polyalkanes and alkenes containing hydrogenated and non-hydrogenated polyalphaolefins, synthetic polyoxyalkylene-derived oils, the United States. It is described in Patent Nos. 3,756,793; 4,191,537; and 5,004,478; and European Patent Application Nos. 356,726 and 382,159.

The carrier fluid can be used in an amount in the range of 35 to 5000 ppm by weight of the hydrocarbon fuel (eg, 50 to 3000 ppm of fuel). When used in fuel concentrates, the carrier fluid may be present in an amount in the range of 20-60% by weight (eg, 30-50% by weight).

Lubricating Oil Compositions The compounds of the present disclosure can be useful as additives in lubricating oils to prevent or reduce engine knocking or pre-ignition events in spark-ignition internal combustion engines.

The concentrations of the compounds of the present disclosure in the lubricating oil composition can range from 0.01 to 15% by weight (eg, 0.5 to 5% by weight) based on the total weight of the lubricating oil composition.

Lubricating viscosity oils (sometimes referred to as "base stocks" or "base oils") are the primary liquid components of a lubricant and are blended with additives and, in some cases, other oils, eg, final lubricants (or final lubricants). Lubricant composition) is produced. Base oils useful for the production of concentrates and the production of lubricating oil compositions can be selected from natural (plant, animal or mineral) and synthetic lubricating oils and mixtures thereof.

The definition of basestock and base oil in this disclosure is found in the American Petroleum Institute (API) Publication 1509 Annex E (“API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils,” December 2016). Is the same as. Group I base stocks contain less than 90% saturated and / or more than 0.03% sulfur and have a viscosity index of greater than or equal to 80 and less than 120 using the test methods specified in Table E-1. .. Group II basestocks contain 90% or more saturated material and 0.03% or less sulfur and have a viscosity index of 80 or more and less than 120 using the test methods specified in Table E-1. Group III basestocks contain 90% or more saturated material and 0.03% or less sulfur and have a viscosity index of 120 or greater using the test methods specified in Table E-1. The base stock of Group IV is polyalphaolefin (PAO). Group V basestock includes all other basestock not included in Group I, II, III, or IV.

Natural oils include animal oils, vegetable oils (eg castor oil and lard oil), and mineral oils. Animal and vegetable oils with excellent thermal oxidation stability can be used. Of the natural oils, mineral oil is preferred. Mineral oils differ greatly with respect to the source of crude oil, for example, whether they are paraffinic, naphthenic, or paraffin-naphthenic mixtures. Oils derived from coal and shale are also useful. Natural oils also depend on the method used in their production and refining, eg, distillation range and whether they are distilled, decomposed, hydrorefined, or solvent extracted.

Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized and interconnected olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers). Polyalphaolefin (PAO) oil-based stocks are commonly used synthetic hydrocarbon oils. As an _{example, PAOs derived from C 8} to C ₁₄ olefins, such as C ₈ , C ₁₀ , C ₁₂ , C ₁₄ olefins or mixtures thereof, can be utilized.

Other useful fluids for use as base oils (base oils) are preferably non-conventional or non-conventional base stocks that are catalytically treated or synthesized to provide high performance properties. Is included.

Non-conventional or non-conventional basestocks / base oils are derived from one or more mixtures of basestocks derived from one or more gas-to-liquid (GTL) materials, as well as natural waxes or waxy feeds. Isomeric / isodewax basestock, mineral oils such as slack wax, natural wax and / or non-mineral oil waxy raw materials, and gas oils, waxy fuel hydrocracking equipment bottoms, waxy raffinates, hydrocracked products, Wax-like substances derived from wax-like stocks such as thermal decomposition products, or non-petroleum-derived wax-like substances such as wax-like substances received from other mineral oils, mineral oils, or coal liquefied or shale oils, and mixtures of such base stocks. include.

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

Base oils typically have a kinematic viscosity at 100 ° C. in the range of 2.5 to 20 mm ² / sec (eg, 3 to 12 mm ² / sec, 4 to 10 mm ² / sec, or 4.5 to 8 mm ² / s). Is.

The lubricating oil compositions of the present book may also include conventional lubricating oil additives for imparting auxiliary functions to provide a finished lubricating oil composition in which these additives are dispersed or dissolved. For example, lubricating oil compositions include antioxidants, ashless dispersants, abrasion resistant agents, cleaning agents such as metal cleaning agents, rust inhibitors, antifogging agents, dehumidifiers, friction modifiers, metal inactivating agents, and injections. It can be blended with descent agents, viscosity modifiers, defoaming agents, co-solvents, package compatibilizers, corrosion inhibitors, dyes, extreme pressure agents and mixtures thereof. Various additives are known and are commercially available. These additives, or similar compounds thereof, can be used in the preparation of the lubricating oil compositions of the present invention by conventional mixing procedures.

Each of the above 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, the functionally effective amount of the ashless dispersant will be sufficient to provide the lubricant with the desired dispersion properties. In general, the concentration of each of these additives, when used, can range from about 0.001 to about 20% by weight, for example from about 0.01 to about 10% by weight, unless otherwise specified.

Examples The following exemplary examples are intended to be non-limiting.

Example 1-45
The test compounds were mixed in gasoline or lubricant and their ability to reduce LSPI events was determined using the test methods described below.

A GM 2.0L LHU 4-cylinder gasoline turbocharged direct injection engine was used for the LSPI test. Each cylinder was equipped with a combustion pressure sensor.

A 6-segment test procedure was used to determine the number of LSPI events that occurred under conditions of an engine speed of 2000 rpm and a load of 275 Nm. The LSPI test condition is run for 28 minutes and each segment is separated by an idle period. The first segment is used for oil conditioning and the number of LSPI events is not counted. Each segment is truncated slightly to eliminate temporary parts. Each truncated segment typically has about 100,000 combustion cycles (25,000 combustion cycles per cylinder). In total, the five truncated segments that count LSPI events have about 500,000 combustion cycles (12,500 combustion cycles per cylinder). Testing may be shortened if the engine is unable to complete all six segments.

The combustion cycle affected by the LSPI was determined by monitoring the peak cylinder pressure (PP) and crank angle at 5% total heat release (AI5). The combustion cycles affected by LSPI are (1) PP with more than 5 standard deviations above the average PP for a particular cylinder and truncated segments, and (2) 5 standards above the average for a particular cylinder and truncated segments. It is defined as having both AI5s that exceed the deviation.

The LSPI frequency is reported as the number of LSPI-affected combustion cycles per million combustion cycles and is calculated as follows.
LSPI frequency = [(total number of LSPI-affected combustion cycles in 5 truncated segments) / (total number of combustion cycles in 5 truncated segments)] x 1,000,000

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

Claims (39)

A fuel composition containing (1) a hydrocarbon fuel that boils in the range of gasoline or diesel exceeds 50 wt%, and (2) a small amount of one or more of the following:
(I) Amino additive, (ii) Amine additive, (iii) Triazole additive, (iv) Benzamidinium additive, (v) Benzoxazole additive or (vi) N = C having the following structure Primary Low Speed Preignition (LSPI) Reduction Additives Containing -X Motif Additives

Here, X ₁ and X ₂ are independently H, C, N, O, or S; and here, X ₁ or X ₂ is independently one or more C _{1 to} C _20. Contains an alkyl group or one or more aromatic groups. The fuel composition according to claim 1, wherein the amino additive is a beta-aminoalkanol, an amino acid, or an amino ester. The fuel composition according to claim 1, wherein the amine additive is an aromatic amine or an aliphatic amine. The fuel composition according to claim 1, wherein the triazole additive is 5,6-dimethylbenzotriazole. Primary LSPI reduction additives include prolinol, aliquots, morphgum, 2-aminobenzimidazole, AHPD, N, N-dimethyl-N-octylbenzamidinium-2-oxide, benzoxazole, 2-methylquinoline-8- The fuel composition according to claim 1, which is an amine or 2-aminobenzoxazole. The fuel composition according to claim 1, wherein the N = CX motif additive is amidine, guanidine, imidazole, benzamidine, benzimidazole, or aminobenzimidazole. Amidines are 1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1, 5-Diazabicyclo [4.3.0] non-5-ene (DBN), 2-phenyl-1H-benzo [d] imidazole, or 1,8-diazabicyclo [5.4.0] -undese-7-ene The fuel composition according to claim 6, which is (DBU). Guanidine is 1,1,3,3-tetramethylguanidine (TMG), 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), 1,5,7-triazabicyclo [4]. .4.0] dece-5-ene (TBD), 1,2-diphenylguanidine, or 7-methyl-1,5,7-triazabicyclo [4.4.0] dece-5-ene (4.4.0] dece-5-ene ( MTBD), the fuel composition of claim 6. The fuel composition according to claim 1, further comprising a secondary LSPI reduction additive comprising an acid additive, a phenol additive, a 1,3 dicarbonyl additive, a hydroxamide additive, an antioxidant additive, or a salicylic acid additive. thing. The fuel composition according to claim 9, wherein the primary LSPI reducing additive and the secondary LSPI reducing additive form a salt. The fuel composition according to claim 9, wherein the acid additive is a fatty acid, an unsaturated acid, an alkyl aromatic acid, an aromatic acid, a hydroxy acid, or an amino acid. Secondary LSPI reduction additives include 2-ethylhexanoate, isostearate, proline, diketone, oleate, toluene, tetralin carboxylate, phenoxide, phenol carboxylate, hydroxy acids, 2-hydroxy-5- (tetracosa-1). , 3,5,7,9,11,13,15,17,19,21,23-dodecine-1-yl) The fuel composition according to claim 9, which is benzoic acid-dihydrogen or ketoester. (1) 90 to 30 wt% organic solvent boiling in the range of 65 ° C to 205 ° C, and (2) 10 to 70 wt% additive component selected from one or more of the following.
Fuel concentrate containing:
(I) Amino additive, (ii) Amine additive, (iii) Triazole additive, (iv) Benzamidinium additive, (v) Benzoxazole additive, or (vi) N = having the following structure CX motif additive

Here, X ₁ and X ₂ are independently H, C, N, O, or S; and here, X ₁ or X ₂ is independently one or more C _{1 to} C _20. Contains an alkyl group or one or more aromatic groups. The fuel concentrate according to claim 13, wherein the amino additive is a beta-aminoalkanol, an amino acid, or an amino ester. The fuel concentrate according to claim 13, wherein the amine additive is an aromatic amine or an aliphatic amine. The fuel concentrate according to claim 13, wherein the triazole additive is 5,6-dimethylbenzotriazole. Primary LSPI reduction additives include prolinol, aliquot, morphgum, 2-aminobenzimidazole, AHPD, N, N-dimethyl-N-octylbenzamidinium-2-oxide, benzoxazole, 2-methylquinoline-8- The fuel concentrate according to claim 13, which is an amine, or 2-aminobenzoxazole. The fuel concentrate according to claim 13, wherein the N = CX motif additive is amidine, guanidine, imidazole, benzamidine, benzimidazole, or aminobenzimidazole. Amidine is 1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1,5 -Diazabicyclo [4.3.0] non-5-ene (DBN), 2-phenyl-1H-benzo [d] imidazole, or 1,8-diazabicyclo [5.4.0] -undese-7-ene ( DBU), the fuel concentrate according to claim 18. Guanidine is 1,1,3,3-tetramethylguanidine (TMG), 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), 1,5,7-triazabicyclo [4]. .4.0] Dece-5-ene (TBD), 1,2-diphenylguanidine, or 7-methyl-1,5,7-triazabicyclo [4.4.0] dece-5-ene (4.4.0] dece-5-ene ( MTBD), the fuel concentrate according to claim 18. The fuel enrichment according to claim 13, further comprising a secondary LSPI reduction additive comprising an acid additive, a phenol additive, a 1,3 dicarbonyl additive, a hydroxamide additive, an antioxidant additive, or a salicylic acid additive. thing. The fuel concentrate according to claim 21, wherein the acid additive is a fatty acid, unsaturated acid, alkyl aromatic acid, aromatic acid, hydroxy acid, or amino acid. 21. The secondary LSPI reducing additive is 2-ethylhexanoate, isostearate, proline, diketone, oleate, toluene, tetralin carboxylate, phenoxide, phenolcarboxylate, hydroxy acid, or ketoester. Fuel concentrate. Lubricating oil composition containing (1) more than 50% by weight of base oil and (2) 0.01 to 15% by weight of components selected from one or more of the following:
(I) Amino additive, (ii) Amine additive, (iii) Triazole additive, (iv) Benzamidinium additive, (v) Benzoxazole additive or (vi) N = C having the following structure Primary Low Speed Preignition (LSPI) Reduction Additives Containing -X Motif Additives

Here, X ₁ and X ₂ are independently H, C, N, O, or S; and here, X ₁ or X ₂ is independently one or more C _{1 to} C _20. Contains an alkyl group or one or more aromatic groups. The lubricating oil composition according to claim 24, wherein the amino additive is a beta-aminoalkanol, an amino acid, or an amino ester. The lubricating oil composition according to claim 24, wherein the amine additive is an aromatic amine or an aliphatic amine. The lubricating oil composition according to claim 24, wherein the triazole additive is 5,6-dimethylbenzotriazole. Primary LSPI reduction additives include prolinol, aliquots, morphgum, 2-aminobenzimidazole, AHPD, N, N-dimethyl-N-octylbenzamidinium-2-oxide, benzoxazole, 2-methylquinoline-8- The lubricating oil composition according to claim 24, which is an amine or 2-aminobenzoxazole. The lubricating oil composition according to claim 24, wherein the N = CX motif additive is amidine, guanidine, imidazole, benzamidine, benzimidazole, or aminobenzimidazole. Amidine is 1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1,5 -Diazabicyclo [4.3.0] non-5-ene (DBN), 2-phenyl-1H-benzo [d] imidazole, or 1,8-diazabicyclo [5.4.0] -undese-7-ene ( DBU), the lubricating oil composition according to claim 29. Guanidine is 1,1,3,3-tetramethylguanidine (TMG), 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), 1,5,7-triazabicyclo [4]. .4.0] dece-5-ene (TBD), 1,2-diphenylguanidine, or 7-methyl-1,5,7-triazabicyclo [4.4.0] dece-5-ene (4.4.0] dece-5-ene ( MTBD), the lubricating oil composition according to claim 29. The lubricant according to claim 24, further comprising a secondary LSPI reducing additive, including an acid additive, a phenolic additive, a 1,3 dicarbonyl additive, a hydroxamide additive, an antioxidant additive, or a salicylic acid additive. Composition. 32. The secondary LSPI reducing additive is 2-ethylhexanoate, isostearate, proline, diketone, oleate, toluene, tetralin carboxylate, phenoxide, phenolcarboxylate, hydroxy acid, or ketoester. Lubricating oil composition. Spark Ignition A method for preventing or reducing slow pre-ignition events in an internal combustion engine, comprising supplying the lubricating oil composition of claim 24 to the engine. 34. The method of claim 34, wherein the spark-ignition internal combustion engine operates at a speed of less than 3000 rpm. 34. The method of claim 34, wherein the spark-ignition internal combustion engine is operated under a load having a brake mean effective pressure of at least 10 bar (1 MPA). Spark ignition A method for preventing or reducing a low-speed pre-ignition event in an internal combustion engine, which comprises supplying the fuel composition according to claim 1 to the engine. 37. The method of claim 37, wherein the spark-ignition internal combustion engine operates at a speed of less than 3000 rpm. 37. The method of claim 37, wherein the spark-ignition internal combustion engine is operated under a load having a brake mean effective pressure of at least 10 bar (1 MPA).