Gasoline fuel composition

Abstract

The use of (a) amino-based deposition control additives and (b) complex esters in gasoline fuel compositions for the purpose of providing synergistic reduction of engine wear in spark-ignition internal combustion engines fueled by said gasoline fuel compositions, wherein (b) the complex ester is obtained by esterification reaction between (A) at least one aliphatic straight-chain or branched C2 to C12 dicarboxylic acid, (B) at least one aliphatic straight-chain or branched polyhydroxy alcohol having 3 to 6 hydroxyl groups and (c) at least one aliphatic straight-chain or branched C1 to C30 monocarboxylic acid (C1) as a chain terminator in the case of an excess of component (B), or at least one aliphatic straight-chain or branched monocarboxylic acid (C2) as a chain terminator in the case of an excess of component (A).

Description

Technical Field

[0001] This invention relates to a gasoline fuel composition, and more particularly to the use of a certain combination of additive components in a gasoline fuel composition for providing a synergistic reduction in engine wear and / or friction. Background Technology

[0002] Government regulations and market demand continue to emphasize fossil fuel conservation in the transportation sector. To meet CO2 emission reduction targets, there is an increasing need for more fuel-efficient vehicles. Therefore, any incremental improvement in fuel economy (FE) is crucial in the automotive industry. It is known that improvements in fuel economy performance in spark-ignition engines can be achieved by reducing the frictional and abrasive properties of the gasoline fuel composition.

[0003] EP3050636B1 discloses the use of complex esters for reducing fuel consumption.

[0004] It has now been surprisingly discovered that the combined use of selected amine-based deposition control additives (DCAs) with selected complex esters in gasoline fuel compositions can provide a synergistic reduction in engine wear and / or friction. Summary of the Invention

[0005] According to the present invention, (a) an amino-based deposition control additive and (b) a complex ester are provided for use in a gasoline fuel composition for the purpose of providing a synergistic reduction of engine wear in a spark-ignition internal combustion engine fueled by said gasoline fuel composition, wherein (b) the complex ester is obtained by an esterification reaction between (A) at least one aliphatic straight-chain or branched C2 to C12 dicarboxylic acid, (B) at least one aliphatic straight-chain or branched polyhydroxy alcohol having 3 to 6 hydroxyl groups and (C) at least one aliphatic straight-chain or branched C1 to C30 monocarboxylic acid (C1) as a chain terminator in the case of an excess of component (B), or at least one aliphatic straight-chain or branched monocarboxylic acid (C2) as a chain terminator in the case of an excess of component (A).

[0006] The present invention further provides the use of (a) an amino-based deposition control additive and (b) a complex ester in a gasoline fuel composition for the purpose of providing synergistic friction reduction in a spark-ignition internal combustion engine fueled by said gasoline fuel composition, wherein (b) the complex ester is obtained by esterification reaction between (A) at least one aliphatic straight-chain or branched C2 to C12 dicarboxylic acid, (B) at least one aliphatic straight-chain or branched polyhydroxy alcohol having 3 to 6 hydroxyl groups and (C) at least one aliphatic straight-chain or branched C1 to C30 monocarboxylic acid (C1) as a chain terminator in the case of an excess of component (B), or at least one aliphatic straight-chain or branched monocarboxylic acid (C2) as a chain terminator in the case of an excess of component (A).

[0007] The present invention further provides a method for providing synergistic reduction of engine wear in a spark-ignition internal combustion engine, the method comprising supplying fuel to the internal combustion engine with a gasoline fuel composition comprising: (a) an amino-based deposition control additive; (b) a complex ester obtainable by esterification reaction between (A) at least one aliphatic straight-chain or branched C2 to C12 dicarboxylic acid, (B) at least one aliphatic straight-chain or branched polyhydroxy alcohol having 3 to 6 hydroxyl groups and (C) at least one aliphatic straight-chain or branched C1 to C30 monocarboxylic acid (C1) as a chain terminator in the presence of an excess of component (B), or at least one aliphatic straight-chain or branched monocarboxylic alcohol (C2) as a chain terminator in the presence of an excess of component (A); and (c) a base fuel suitable for an internal combustion engine.

[0008] The present invention further provides a method for providing a synergistic reduction of friction in a spark-ignition internal combustion engine, the method comprising supplying fuel to the internal combustion engine with a gasoline fuel composition comprising:

[0009] (a) Amino-based deposition control additives;

[0010] (b) A complex ester obtainable by esterification of (A) at least one aliphatic straight-chain or branched C2 to C12 dicarboxylic acid, (B) at least one aliphatic straight-chain or branched polyhydroxy alcohol having 3 to 6 hydroxyl groups, and (C) at least one aliphatic straight-chain or branched C1 to C30 monocarboxylic acid (C1) as a chain terminator in the case of an excess of component (B), or at least one aliphatic straight-chain or branched monocarboxylic alcohol (C2) as a chain terminator in the case of an excess of component (A); and

[0011] (c) Base fuel suitable for internal combustion engines. Attached Figure Description

[0012] Figure 1-18 This is a graphical representation of the results shown in Tables 1 and 2 above.

[0013] Figure 1 This is a graphical representation of the average friction coefficient of the fuels in Examples 1-4 at 30°C.

[0014] Figure 2 This is a graphical representation of the average wear data of the fuels in Examples 1-4 at 30°C.

[0015] Figure 3 This is a graphical representation of the average friction coefficient of the fuels in Examples 1-4 at 40°C.

[0016] Figure 4This is a graphical representation of the average wear data of the fuels in Examples 1-4 at 40°C.

[0017] Figure 5 This is a graphical representation of the friction coefficient data of the fuels in Examples 1, 5, and 6 at 30°C.

[0018] Figure 6 This is a graphical representation of the average wear data of the fuels in Examples 1, 5, and 6 at 30°C.

[0019] Figure 7 This is a graphical representation of the friction coefficient data of the fuels in Examples 1, 5, and 6 at 40°C.

[0020] Figure 8 This is a graphical representation of the average wear data of the fuels in Examples 1, 5, and 6 at 40°C.

[0021] Figure 9 This is a graphical representation of the average coefficient of friction of the fuels in Examples 1, 11, 12 and 13 at 30°C.

[0022] Figure 10 This is a graphical representation of the average wear data of the fuels in Examples 1, 11, 12 and 13 at 30°C.

[0023] Figure 11 This is a graphical representation of the average coefficient of friction of the fuels in Examples 1, 11, 12 and 13 at 40°C.

[0024] Figure 12 This is a graphical representation of the average wear data of the fuels in Examples 1, 11, 12 and 13 at 40°C.

[0025] Figure 13 This is a graphical representation of the average friction coefficient of the fuels in Examples 1, 2, and 11 at 30°C.

[0026] Figure 14 This is a graphical representation of the average wear data of the fuels in Examples 1, 2 and 11 at 30°C.

[0027] Figure 15 This is a graphical representation of the average coefficient of friction of the fuels in Examples 1, 8, and 13 at 30°C.

[0028] Figure 16 This is a graphical representation of the average wear data of the fuels in Examples 1, 8, and 13 at 30°C.

[0029] Figure 17 This is a graphical representation of the average friction coefficient data of the fuels in Examples 14-19 at 30°C.

[0030] Figure 18This is a graphical representation of the wear track data of Examples 14-19 at 30°C. Detailed Implementation

[0031] The gasoline fuel composition described herein comprises a base fuel suitable for spark-ignition internal combustion engines, an amino-based deposition control additive, and a complex ester. The base fuel suitable for spark-ignition internal combustion engines is a gasoline base fuel, and therefore the fuel composition described herein is a gasoline fuel composition.

[0032] According to the present invention, uses and methods for providing a synergistic reduction in engine wear are provided. As used herein, the term "synergistic reduction in engine wear" means that the reduction in engine wear obtained with a fuel composition of the present invention comprising a combination of an amino-based deposition control additive and a complex ester as described herein is greater than the simple sum of the reduction in engine wear obtained with a similar fuel formulation comprising only an amino-based deposition control additive (i.e., without a complex ester) and the reduction in engine wear obtained with a similar fuel formulation comprising only a complex ester (i.e., without an amino-based deposition control additive). In other words, the reduction in engine wear obtained via the uses and methods of the present invention is synergistic rather than additive. In the context of this aspect of the invention, the term "reduction" can be, for example, 0.05% or more, preferably 0.1% or more, more preferably 0.2% or more, even more preferably 0.5% or more, especially 1% or more, more particularly 2% or more, and even more particularly 5% or more of the engine wear provided by a similar fuel formulation comprising one of the amino-based deposition control additives or complex esters according to the present invention. The reduction in engine wear can even be as high as 20% of the engine wear provided by a similar fuel formulation containing one of the amino-based deposition control additives or complex esters.

[0033] As used herein, the term 'synergistic reduction of friction' means that the reduction of friction obtained with the fuel composition of the present invention, comprising a combination of an amino-based deposition control additive and a complex ester as described herein, is greater than the simple sum of the reduction of friction obtained with similar fuel formulations comprising only an amino-based deposition control additive (i.e., without a complex ester) and the reduction of friction obtained with similar fuel formulations comprising only a complex ester (i.e., without an amino-based deposition control additive). In other words, the reduction of friction obtained via the use and method of the present invention is synergistic rather than additive. In the context of this aspect of the invention, the term "reduction" can be, for example, 0.05% or more, preferably 0.1% or more, more preferably 0.2% or more, even more preferably 0.5% or more, especially 1% or more, more particularly 2% or more, even more particularly 5% or more, of the friction provided by similar fuel formulations comprising either an amino-based deposition control additive or a complex ester according to the present invention. The reduction of friction can even be as high as 30% of the friction provided by similar fuel formulations containing either an amino-based deposition control additive or a complex ester.

[0034] The first component used herein is an amino-based deposition control additive. As used herein, the term "deposition control additive" refers to a component also known in the art as a detergent. This amino-based deposition control additive typically has at least one hydrophobic hydrocarbon group with a number-average molecular weight (Mn) of 85 to 20,000 and at least one polar portion selected from mono- or poly-amino groups having up to six nitrogen atoms, wherein at least one of these nitrogen atoms has basic properties.

[0035] The number-average molecular weight (Mn) of the hydrophobic hydrocarbon groups in the aforementioned amino-based deposition control additives, which ensure sufficient solubility in the base fluid, is 85 to 20,000, particularly 113 to 10,000, and especially 300 to 5,000. Typical hydrophobic hydrocarbon groups, especially those bonded to polar moieties, include polyolefins, such as polypropylene, polybutene, and polyisobutylene, each with an Mn of 300 to 5,000, preferably 500 to 2,500, more preferably 700 to 2,300, and especially 700 to 1,000. The preferred hydrophobic hydrocarbon group is polyisobutylene.

[0036] In one embodiment of this document, the amino-based deposition control additive is an amine substituted with an aliphatic hydrocarbon group having at least one basic nitrogen atom, wherein the number-average molecular weight of the hydrocarbon group is about 700 to 3,000.

[0037] Non-limiting examples of these amino-based deposition control additives include the following:

[0038] Additives containing mono- or polyamino groups (Al) are preferably polyolefin monoamines or polyolefin polyamines based on polypropylene or conventional (i.e., predominantly internal double bonds) polybutene or polyisobutylene with a Mn of 300 to 5000. When polybutene or polyisobutylene predominantly having internal double bonds (typically at the β and γ positions) is used as a raw material for the preparation of additives, possible preparation routes are by chlorination and subsequent amination, or by oxidation of the double bonds with air or ozone to obtain carbonyl or carboxyl compounds and subsequent amination under reducing (hydrogenating) conditions. The amines used for amination here can be, for example, ammonia, monoamines, or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine. Corresponding additives based on polypropylene are specifically described in WO-A-94 / 24231.

[0039] Another preferred additive containing a monoamino group is a hydrogenated product of the reaction of polyisobutylene with nitrogen oxides or a mixture of nitrogen oxides and oxygen with an average degree of polymerization of 5 to 100, particularly as described in WO-A-97 / 03946.

[0040] Another preferred additive containing a single amino group is a compound that can be obtained from polyisobutylene epoxide by reacting it with an amine and subsequently dehydrating and reducing the amino alcohol, particularly as described in DE-A-19620262.

[0041] The preferred amino-based deposition control additive used herein is polyisobutylene amine. An example of a commercially available polyisobutylene amine deposition control additive is the polyisobutylene amine deposition control additive available from BASF under the trade name Kerocom PIBA03.

[0042] The amino-based deposition control additive is preferably present in the fuel composition at a level of 50-2000 ppm, more preferably 90-1500 ppm, even more preferably 150-1000 ppm, and especially in the range of 170-950 ppm, based on the weight of the total fuel composition.

[0043] In a particularly preferred embodiment herein, the amino-based deposition control additive is present in the fuel composition at a level ranging from 179 to 920 ppm by weight of the total fuel composition.

[0044] The second basic component of this article is a complex ester. The complex ester used in this article can be obtained by esterification reaction between (A) at least one aliphatic straight-chain or branched C2 to C12 dicarboxylic acid, (B) at least one aliphatic straight-chain or branched polyhydroxy alcohol having 3 to 6 hydroxyl groups and (C) at least one aliphatic straight-chain or branched C1 to C30 monocarboxylic acid (C1) as a chain terminator in the case of an excess of component (B), or at least one aliphatic straight-chain or branched monocarboxylic alcohol (C2) as a chain terminator in the case of an excess of component (A).

[0045] The aliphatic dicarboxylic acids of component (A) may be branched or preferably linear; they may be unsaturated or preferably saturated. Typical examples of component (A) are oxalic acid, malonic acid, succinic acid, (Z)-butenic acid, (E)-butenic acid, glutaric acid, pent-2-eneic acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, dodecano-2-eneic acid, and (2E,4E)-hex-2,4-dieneic acid. Mixtures of the above aliphatic dicarboxylic acids may also be used.

[0046] In a preferred embodiment, at least one aliphatic dicarboxylic acid of component (A) is selected from aliphatic straight-chain C6 to C10 dicarboxylic acids, which are preferably saturated. Adipic acid and sebacic acid are most preferred.

[0047] In a particularly preferred embodiment herein, at least one aliphatic dicarboxylic acid of component (A) is adipic acid.

[0048] The aliphatic polyhydroxy alcohols of component (B) can be branched or linear; they can be unsaturated or preferably saturated; they can contain 3 to 12, preferably 3 to 8, especially 3 to 6 carbon atoms, and preferably 3, 4, or 5 hydroxyl groups. Typical examples of component (B) are trimethylolethane, trimethylolpropane, trimethylolbutane, sorbitol, glycerol, and pentaerythritol. Mixtures of the above aliphatic polyhydroxy alcohols may also be used.

[0049] In a preferred embodiment, at least one aliphatic polyhydroxy alcohol of component (B) is selected from glycerol, trimethylolpropane and pentaerythritol.

[0050] In another preferred embodiment, at least one aliphatic polyhydroxy alcohol of component (B) is selected from trimethylolpropane and pentaerythritol.

[0051] In a particularly preferred embodiment herein, at least one aliphatic polyhydroxy alcohol of component (B) is trimethylolpropane.

[0052] Depending on whether component (B) is used in excess compared to component (A) in the esterification reaction, resulting in residual free hydroxyl groups, or component (A) is used in excess compared to component (B) in the esterification reaction, resulting in residual free carboxyl groups, a chain terminator (C1) or (C2) is used in the synthesis of the aforementioned complex ester. The carboxylic acid ester component (C1) converts the residual free hydroxyl groups into additional carboxylic acid ester groups. The monohydric alcohol component (C2) converts the residual free carboxyl groups into additional carboxylic acid ester groups.

[0053] The aliphatic monocarboxylic acids of component (C1) can be branched or straight-chain, and they can be unsaturated or preferably saturated. Typical examples of component (C1) are formic acid, acetic acid, propionic acid, 2,2-dimethylpropionic acid (neopentanoic acid), hexanoic acid, octanoic acid (linolenic acid), 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, nonanoic acid, decanoic acid (linolenic acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid, trans-linoleic acid, erucic acid, arachidic acid, benzanoic acid, tetracosanoic acid, and ceric acid. The above monocarboxylic acids, including so-called fatty acids, can be synthetic or naturally derived. Mixtures of the above aliphatic monocarboxylic acids can also be used.

[0054] In a preferred embodiment, at least one aliphatic monocarboxylic acid of component (C1) is selected from aliphatic straight-chain or branched C8 to C18 monocarboxylic acids.

[0055] In a particularly preferred embodiment, at least one aliphatic monocarboxylic acid of component (C1) is selected from aliphatic straight-chain or branched C8 to C10 monocarboxylic acids.

[0056] The aliphatic monohydric alcohols of component (C2) can be branched or linear; they can be unsaturated, or preferably saturated. Typical examples of component (C2) are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, n-nonanol, 2-propylheptanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, isotrigine, n-tetradecanol, isotetradecanol, n-hexadecanol, n-octadecanol, isooctadecanol, and n-eicosanool. Mixtures of the above monohydric alcohols may also be used. Prior to being used as chain terminators for the preparation of the aforementioned complex esters, the monohydric alcohols may have been alkoxylated with hydrocarbon epoxides such as ethylene oxide, propylene oxide, and / or butane oxide to produce single-terminated polyethers.

[0057] In a preferred embodiment, at least one aliphatic monohydric alcohol of component (C2) is selected from straight-chain or branched C8-C18 alkanols.

[0058] In a preferred embodiment of the present invention, at least one aliphatic dicarboxylic acid of component (A) is selected from preferably saturated aliphatic straight-chain C6-C10 dicarboxylic acids, at least one aliphatic polyhydroxy alcohol of component (B) is selected from glycerol, trimethylolpropane and pentaerythritol, and the chain terminator (C) is at least one aliphatic monocarboxylic acid component (C1) selected from aliphatic straight-chain or branched C8 to C18 monocarboxylic acids.

[0059] In a particularly preferred embodiment of the invention, at least one aliphatic dicarboxylic acid of component (A) is selected from bisaccharide or sebacic acid, at least one aliphatic polyhydroxy alcohol of component (B) is trimethylolpropane or pentaerythritol, and the chain terminator (C) is an aliphatic monocarboxylic acid component (C1) selected from aliphatic straight-chain or branched C8 to C18 monocarboxylic acids.

[0060] In a particularly preferred embodiment of the invention, at least one aliphatic dicarboxylic acid of component (A) is selected from bisaccharide, at least one aliphatic polyhydroxy alcohol of component (B) is trimethylolpropane, and the chain terminator (C) is an aliphatic monocarboxylic acid component (C1) selected from aliphatic straight-chain or branched C8 to C10 monocarboxylic acids.

[0061] The synthesis of complex esters is known in the art. Further details of the synthesis can be found in EP 3060 636B1, which is incorporated herein by reference. It can be prepared by mixing and reacting components (A) and (B), followed by reacting an intermediate ester formed from (A) with component (C). Alternatively, it can also be prepared by simultaneously mixing and reacting components (A), (B), and (C).

[0062] The complex ester mentioned is typically composed of a component (A) of at least two molecular units, a component (B) of at least three molecular units, and a chain terminator (C) of a corresponding number of molecular units, or is composed of a component (B) of at least two molecular units, a component (A) of at least three molecular units, and a chain terminator (C) of a corresponding number of molecular units.

[0063] In a preferred embodiment, the composite ester mentioned comprises a component (A) of 2 to 9 molecular units, particularly 2 to 5 molecular units, and a component (B) of 3 to 10 molecular units, particularly 3 to 6 molecular units, wherein component (B) is in excess compared to component (A), and wherein the remaining free hydroxyl groups of (B) are completely or partially capped by the corresponding number of molecular units of component (C1).

[0064] In another preferred embodiment, the aforementioned complex ester comprises a component (A) of 3 to 10 molecular units, particularly 3 to 6 molecular units, and a component (B) of 2 to 9 molecular units, particularly 2 to 5 molecular units, wherein component (A) is in excess relative to component (B), and wherein the remaining free carboxyl groups of (A) are completely or partially capped by the corresponding number of molecular units of component (C2).

[0065] Typical composite esters used in this invention consist of a component (A) of 3 or 4 molecular units, particularly at least one aliphatic straight-chain C6 to C10 dicarboxylic acid (such as adipic acid and / or sebacic acid), or a component (B) of 4 or 5 molecular units, particularly glycerol, trimethylolpropane and / or pentaerythritol, and a component (C1) of 6 to 12 molecular units, particularly at least one aliphatic straight-chain or branched C8 to C18 monocarboxylic acid (such as octanoic acid, 2-ethylhexanoic acid, 3,4,4-trimethylhexanoic acid, nonanoic acid, decanoic acid and / or isostearic acid).

[0066] The particularly preferred composite esters used in this article are Examples 2 and 3 of EP 3060636B1.

[0067] In one embodiment of this document, the composite ester used herein is Example 2 of EP3060636B1.

[0068] In another embodiment of this document, the composite ester used herein is Example 3 of EP3060636B1.

[0069] The composite ester mentioned is oil-soluble, which means that when mixed with mineral oil and / or fuel in weight ratios of 10:90, 50:50 and 90:10, the composite ester does not show phase separation after standing at room temperature for 24 hours for at least two of the three weight ratios of 10:90, 50:50 and 90:10.

[0070] Typically, the amount of the at least one complex ester in the gasoline fuel composition herein is 10-5000 ppm by weight, more preferably 20-2000 ppm by weight, even more preferably 30-1000 ppm by weight, especially 40-500 ppm by weight, for example 50-300 ppm by weight.

[0071] In one embodiment of the invention, the amount of the at least one complex ester in the gasoline fuel composition herein is 30-352 ppm by weight of the gasoline fuel composition.

[0072] In a preferred embodiment of the invention, an amino-based deposition control additive is present in the fuel composition at a level in the range of 179-920 ppm by weight of the total fuel composition, and at least one complex ester is present in the fuel composition at a level in the range of 30-352 ppm by weight of the gasoline fuel composition.

[0073] In a particularly preferred embodiment of the invention, an amino-based deposition control additive is present in the fuel composition at a level in the range of 179-920 ppm by weight of the total fuel composition, and at least one complex ester is present in the fuel composition at a level in the range of 30-352 ppm by weight of the gasoline fuel composition, and the weight ratio of the amino-based deposition control additive to at least one complex ester is in the range of 10:1 to 2:1.

[0074] The amino-based deposition control additive and complex ester can be added to gasoline base fuel individually or in the form of a fuel additive package (also known as a gasoline performance package). This package is a fuel additive concentrate and part of an additive blend. The additive blend is then added to the gasoline base fuel to produce a gasoline fuel composition.

[0075] Preferably, the weight ratio of the amino-based deposition control additive to the complex ester is in the range of 10:1 to 1:1, more preferably in the range of 10:1 to 2:1.

[0076] In one embodiment of the invention, the weight ratio of the amino-based deposition control additive to the complex ester is in the range of 8:1 to 2:1.

[0077] In another embodiment of the invention, the weight ratio of the amino-based deposition control additive to the complex ester is in the range of 6:1 to 2:1.

[0078] In the liquid fuel composition of the present invention, if the base fuel used is gasoline, the gasoline can be any gasoline suitable for spark-ignition (petroleum) type internal combustion engines known in the art, including automobile engines and other types of engines, such as off-road and aircraft engines. The gasoline used as the base fuel in the liquid fuel composition of the present invention can also conveniently be referred to as 'base gasoline'.

[0079] Gasoline typically contains a mixture of hydrocarbons with boiling points ranging from 25°C to 230°C (EN-ISO 3405), with the optimal range and distillation profiles generally varying depending on climate and season. The hydrocarbons in gasoline can be obtained by any means known in the art; conveniently, hydrocarbons can be obtained in any known manner from straight-run gasoline, synthetically produced aromatic mixtures, thermally or catalytically cracked hydrocarbons, hydrocracking petroleum fractions, catalytically reformed hydrocarbons, or mixtures thereof.

[0080] The specific distillation profile, hydrocarbon composition, research octane number (RON), and motor octane number (MON) of gasoline are not critical.

[0081] Conveniently, the research octane number (RON) of the gasoline can be at least 80, for example, in the range of 80 to 110. Preferably, the RON of the gasoline will be at least 90, for example, in the range of 90 to 110. More preferably, the RON of the gasoline will be at least 91, for example, in the range of 91 to 105. Even more preferably, the RON of the gasoline will be at least 92, for example, in the range of 92 to 103. Even more preferably, the RON of the gasoline will be at least 93, for example, in the range of 93 to 102. And most preferably, the RON of the gasoline will be at least 94, for example, in the range of 94 to 100 (DIN EN ISO 5163). The motor octane number (MON) of the gasoline can conveniently be at least 70, for example, in the range of 70 to 110. Preferably, the MON of the gasoline will be at least 75, for example, in the range of 75 to 105. More preferably, the MON of the gasoline will be at least 80, for example, in the range of 80 to 100. Most preferably, the MON of the gasoline will be at least 82, for example, in the range of 82 to 95 (DIN EN ISO 5163). EN ISO 5163).

[0082] Typically, gasoline contains components selected from one or more of the following groups: saturated hydrocarbons, alkenes, aromatics, and oxidized hydrocarbons. Conveniently, gasoline may contain a mixture of saturated hydrocarbons, alkenes, aromatics, and optionally oxidized hydrocarbons.

[0083] Typically, the olefin content of gasoline is in the range of 0-40% by volume based on gasoline (ASTM D1319); preferably, the olefin content of gasoline is in the range of 0-30% by volume based on gasoline, and more preferably, the olefin content of gasoline is in the range of 0-20% by volume based on gasoline.

[0084] Typically, the aromatic content of gasoline is in the range of 0-70% by volume based on gasoline (ASTM D1319), for example, the aromatic content of gasoline is in the range of 10-60% by volume based on gasoline; preferably, the aromatic content of gasoline is in the range of 0-50% by volume based on gasoline, for example, the aromatic content of gasoline is in the range of 10-50% by volume based on gasoline.

[0085] Based on gasoline, the benzene content of the gasoline is at most 10% by volume, more preferably at most 5% by volume, and particularly at most 1% by volume.

[0086] The gasoline preferably has a low or ultra-low sulfur content, for example, up to 1000 ppmw (parts per million by weight), preferably not more than 500 ppmw, more preferably not more than 100 ppmw, even more preferably not more than 50 ppmw, and most preferably not more than even 10 ppmw.

[0087] The gasoline also preferably has a low total lead content, such as up to 0.005 g / l, and most preferably is lead-free, with no lead compounds added to it (i.e., lead-free).

[0088] When gasoline contains oxidized hydrocarbons, at least a portion of the non-oxidized hydrocarbons will be replaced with oxidized hydrocarbons. Based on gasoline, the oxygen content of the gasoline can be up to 35% by weight (EN 1601) (e.g., ethanol itself). For example, the oxygen content of the gasoline can be up to 25% by weight, preferably up to 10% by weight. Conveniently, the concentration of oxygenated compounds will have a minimum concentration selected from any one of 0% by weight, 0.2% by weight, 0.4% by weight, 0.6% by weight, 0.8% by weight, 1.0% by weight, and 1.2% by weight, and a maximum concentration selected from any one of 5% by weight, 4.5% by weight, 4.0% by weight, 3.5% by weight, 3.0% by weight, and 2.7% by weight.

[0089] Examples of oxidized hydrocarbons that can be incorporated into gasoline include alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, and oxygen-containing heterocyclic compounds. Preferably, the oxidized hydrocarbons that can be incorporated into gasoline are selected from alcohols (such as methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, isobutanol and 2-butanol), ethers (preferably ethers containing 5 or more carbon atoms per molecule, such as methyl tert-butyl ether and ethyl tert-butyl ether), and esters (preferably esters containing 5 or more carbon atoms per molecule); a particularly preferred oxidized hydrocarbon is ethanol.

[0090] When oxidized hydrocarbons are present in gasoline, the amount of oxidized hydrocarbons in the gasoline can vary within a wide range. For example, gasolines containing a larger proportion of oxidized hydrocarbons are currently commercially available in countries such as Brazil and the United States, such as ethanol itself and E85, as well as gasolines containing a smaller proportion of oxidized hydrocarbons, such as E10 and E5. Thus, gasoline can contain up to 100% by volume of oxidized hydrocarbons. This document also includes E100 fuel, such as that used in Brazil. Preferably, the amount of oxidized hydrocarbons present in gasoline is selected from the following amounts: up to 85% by volume; up to 70% by volume; up to 65% by volume; up to 30% by volume; up to 20% by volume; up to 15% by volume; and up to 10% by volume, depending on the desired final formulation of the gasoline. Conveniently, gasoline can contain at least 0.5% by volume, 1.0% by volume, or 2.0% by volume of oxidized hydrocarbons.

[0091] Examples of suitable gasoline include gasoline with an olefin content of 0-20% by volume (ASTM D1319), an oxygen content of 0% to 5% by weight (EN 1601), an aromatic content of 0-50% by volume (ASTM D1319), and a benzene content of up to 1% by volume.

[0092] Also applicable here are gasoline blends that may be derived from biological sources. Examples of such gasoline blends can be found in WO2009 / 077606, WO2010 / 028206, WO2010 / 000761, European Patent Application Nos. 09160983.4, 09176879.6, 09180904.6 and U.S. Patent Application Serial No. 61 / 312307.

[0093] Although not critical to the present invention, the base gasoline or gasoline composition of the present invention may conveniently contain one or more optional fuel additives in addition to the aforementioned essentially amino-based deposit control additives and complex esters. The concentration and properties of the optional fuel additives that may be included in the base gasoline or gasoline composition of the present invention are not critical. Non-limiting examples of suitable types of fuel additives that may be included in the base gasoline or gasoline composition of the present invention include antioxidants, corrosion inhibitors, deposit control additives / detergents other than the aforementioned amino-based deposit control additives, demisting agents, antiknock additives, metal deactivators, valve seat depression protectant compounds, dyes, solvents, carrier fluids, diluents, and markers. Examples of suitable such additives are generally described in U.S. Patent No. 5,855,629.

[0094] Conveniently, the fuel additive can be blended with one or more solvents to form an additive concentrate, which can then be mixed with the base gasoline or gasoline composition of the present invention.

[0095] The concentration of any optional additives (active substances) present in the base gasoline or gasoline composition of the present invention is preferably up to 1% by weight, more preferably in the range of 5-2000 ppmw, advantageously in the range of 300-1500 ppmw, such as 300-1000 ppmw.

[0096] As mentioned above, the gasoline composition may also contain synthetic or mineral carrier oils and / or solvents.

[0097] The invention will be further understood through the following examples. Unless otherwise stated, all amounts and concentrations disclosed in the examples are based on the weight of a fully formulated fuel composition.

[0098] Example

[0099] In the following examples, two friction modifiers are used. FM1 is a complex ester as disclosed in Example 3 of EP3060636B1. FM2 is a friction modifier (not having the complex ester structure mentioned above) commercially available from BASF under the trade name Kerocom FM38.

[0100] In the examples shown, Kerocom PIBA03 deposit control additive, commercially available from BASF, was used. The base fuel in Examples 1-13 was isooctane. Isooctane is a component of gasoline and is used as a reference base fuel in Examples 1-13 herein. The base fuel in Examples 14-19 was a standard E0 gasoline base fuel meeting EN228 specifications. Tables 1 and 2 show the relative amounts (in ppm) of various additives (FM1, FM2, PIBA deposit control additive) in each fuel composition. Tested using the HFRR method (using ASTM D6079 test method) at 30°C, 40°C, and 50°C; 200 g (P 平均值 The coefficient of friction of each fuel composition was measured at a pressure of 0.55 GPa, 75 min, 50 Hz, and a stroke length of 1 mm. The friction results are shown in Table 1 below. The wear tracks of each fuel composition were also measured using the HFRR method. The wear track results are shown in Table 2 below.

[0101] Table 1 (Friction Coefficient Data)

[0102] Example fuel 30℃ 40℃ 50℃ 1* Isooctane 0.71 0.61 1.0 2* FM1 (30ppm) 0.55 0.63 0.64 3* FM1 (90ppm) 0.49 0.31 0.29 4* FM1 (270ppm) 0.27 0.31 0.32 5* PIBA (179ppm) 0.60 0.60 0.85 6* PIBA (920ppm) 0.35 0.34 0.32 7* FM2 (30ppm) 0.45 0.53 0.64 8* FM2 (75ppm) 0.46 NM NM 9* FM2 (90ppm) 0.41 0.41 0.39 10* FM2 (270ppm) 0.23 0.23 0.23 11 <![CDATA[FM1(30ppm)+PIBA(179ppm) 1 ]]> 0.35 0.23 0.23 12 <![CDATA[FM1(90ppm)+PIBA(920ppm) 2 ]]> 0.25 0.27 0.27 13* FM2 (75ppm) + PIBA (233ppm) 0.40 0.45 0.48 14* E0 gasoline 1.21 NM NM 15* FM1 (90ppm) 0.33 NM NM 16* FM1 (352ppm) 0.28 NM NM 17* PIBA (920ppm) 0.27 NM NM 18 <![CDATA[FM1(90ppm)+PIBA(920ppm) 2 ]]> 0.24 NM NM 19 <![CDATA[FM1(352ppm)+PIBA(699ppm) 3 ]]> 0.22 NM NM

[0103] Nm = Unmeasured

[0104] *Comparative Examples

[0105] 1. Example 11, representing a PIBA to FM1 weight ratio of 6:1.

[0106] 2. Examples 12 and 18, representing a PIBA to FM1 weight ratio of 10:1.

[0107] 3. Example 19, representing a PIBA to FM1 weight ratio of 2:1.

[0108] Table 2 (Average value of ball wear)

[0109]

[0110]

[0111] Nm = Unmeasured

[0112] *Comparative Examples

[0113] 1. Example 11, representing a PIBA to FM1 weight ratio of 6:1.

[0114] 2. Examples 12 and 18, representing a PIBA to FM1 weight ratio of 10:1.

[0115] 3. Example 19, representing a PIBA to FM1 weight ratio of 2:1.

[0116] Figure 1-18 This is a graphical representation of the results shown in Tables 1 and 2 above.

[0117] Figure 1 This is a graphical representation of the average friction coefficient of the fuels in Examples 1-4 at 30°C.

[0118] Figure 2 This is a graphical representation of the average wear data of the fuels in Examples 1-4 at 30°C.

[0119] Figure 3 This is a graphical representation of the average friction coefficient of the fuels in Examples 1-4 at 40°C.

[0120] Figure 4 This is a graphical representation of the average wear data of the fuels in Examples 1-4 at 40°C.

[0121] Figure 5 This is a graphical representation of the friction coefficient data of the fuels in Examples 1, 5, and 6 at 30°C.

[0122] Figure 6 This is a graphical representation of the average wear data of the fuels in Examples 1, 5, and 6 at 30°C.

[0123] Figure 7 This is a graphical representation of the friction coefficient data of the fuels in Examples 1, 5, and 6 at 40°C.

[0124] Figure 8 This is a graphical representation of the average wear data of the fuels in Examples 1, 5, and 6 at 40°C.

[0125] Figure 9 This is a graphical representation of the average coefficient of friction of the fuels in Examples 1, 11, 12 and 13 at 30°C.

[0126] Figure 10 This is a graphical representation of the average wear data of the fuels in Examples 1, 11, 12 and 13 at 30°C.

[0127] Figure 11 This is a graphical representation of the average coefficient of friction of the fuels in Examples 1, 11, 12 and 13 at 40°C.

[0128] Figure 12This is a graphical representation of the average wear data of the fuels in Examples 1, 11, 12 and 13 at 40°C.

[0129] Figure 13 This is a graphical representation of the average friction coefficient of the fuels in Examples 1, 2, and 11 at 30°C.

[0130] Figure 14 This is a graphical representation of the average wear data of the fuels in Examples 1, 2 and 11 at 30°C.

[0131] Figure 15 This is a graphical representation of the average coefficient of friction of the fuels in Examples 1, 8, and 13 at 30°C.

[0132] Figure 16 This is a graphical representation of the average wear data of the fuels in Examples 1, 8, and 13 at 30°C.

[0133] Figure 17 This is a graphical representation of the average friction coefficient data of the fuels in Examples 14-19 at 30°C.

[0134] Figure 18 This is a graphical representation of the wear track data of Examples 14-19 at 30°C.

[0135] discuss

[0136] As shown in Tables 1 and 2 and Figure 1-18 As can be seen from the data, the combination of PIBA deposition control additive and complex ester (FM1) in the gasoline fuel composition according to the present invention provides a synergistic reduction in engine wear and friction. Tables 1 and 2 and Figure 1-18 It was also shown that the combination of PIBA deposition control additive and a different friction modifier (FM2) that is not a composite ester did not provide a synergistic reduction in engine wear and friction. Even two or three times the amount of the composite ester (FM1) itself (without the PIBA deposition control additive) did not achieve the same good results in reducing friction and wear compared to the compositions of the present invention containing both the composite ester (FM1) and the PIBA deposition control additive. Therefore, when combined with the PIBA deposition control additive, a small amount of the composite ester (FM1) can be used to provide a synergistic reduction in friction and wear.

Claims

1. The use of (a) an amino-based deposition control additive and (b) a complex ester in a gasoline fuel composition for the purpose of providing a synergistic reduction of engine wear in a spark-ignition internal combustion engine fueled by said gasoline fuel composition, wherein (b) the complex ester is formed by (A) at least one aliphatic straight-chain or branched C2 to C12 dicarboxylic acid, (B) at least one aliphatic straight-chain or branched polyhydroxy alcohol having 3 to 6 hydroxyl groups, and (C) at least one aliphatic straight-chain or branched C1 to C30 monocarboxylic acid as a chain terminator in the case of an excess of component (B), or at least one aliphatic straight-chain or branched monocarboxylic acid as a chain terminator in the case of an excess of component (A). The additive is obtained by esterification of a chain or branched monohydric C1 to C30 alcohol, wherein the amino-based deposition control additive is an amine substituted with an aliphatic hydrocarbon group having at least one basic nitrogen atom, wherein the number average molecular weight of the hydrocarbon group is 700 to 3,000, wherein the at least one complex ester is present in the gasoline fuel composition in an amount of 10-5000 ppmw based on the weight of the gasoline fuel composition, wherein the amino-based deposition control additive is present at a level of 50-2000 ppm based on the weight of the gasoline fuel composition, and the weight ratio of the amino-based deposition control additive to the complex ester is in the range of 10:1 to 1:

1.

2. The use according to claim 1, wherein component (A) is selected from aliphatic straight-chain C6 to C10 dicarboxylic acids.

3. The use according to claim 1 or 2, wherein component (B) is selected from glycerol, trimethylolpropane and pentaerythritol.

4. The use according to claim 1 or 2, wherein component (C) is selected from (C1) aliphatic straight-chain or branched C8 to C18 monocarboxylic acids, or from (C2) straight-chain or branched C8 to C18 alkanols.

5. The use according to claim 1 or 2, wherein the composite ester comprises 2 to 9 molecular units of component (A) and 3 to 10 molecular units of component (B), wherein component (B) is in excess compared to component (A), and the remaining free hydroxyl groups of (B) are completely or partially capped with a corresponding number of molecular units of component (C1).

6. The use according to claim 1 or 2, wherein the complex ester comprises 3 to 10 molecular units of component (A) and 2 to 9 molecular units of component (B), wherein component (A) is in excess compared to component (B), and the remaining free carboxyl groups of (A) are completely or partially capped with a corresponding number of molecular units of component (C2).

7. The use according to claim 1 or 2, wherein the amino-based deposition control additive is polyisobutyleneamine.

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