Fuel composition

Abstract

A fuel composition comprising: (i) a base fuel suitable for use in an internal combustion engine; and (ii) a blend of a first monoalkylalkenyl succinate and a second monoalkylalkenyl succinate, wherein the first monoalkylalkenyl succinate and the second monoalkylalkenyl succinate each have the following formula (I) or (II) or are an isomer mixture of the following formula (I) and (II): wherein R is a linear or branched alkenyl group containing 4 to 30 carbon atoms, and R1 is a linear or branched C1 to C8 alkyl group; and wherein the first monoalkylalkenyl succinate is different from the second monoalkylalkenyl succinate. It has been found that the fuel composition of the present invention synergistically reduces engine wear.

Description

Technical Field

[0001] This invention relates to a liquid fuel composition, and more particularly to a liquid fuel composition with improved wear characteristics. The invention also relates to the use of certain combinations of additive components in a liquid fuel composition for synergistically reducing engine wear. Background Technology

[0002] Consumers of fuel products are seeking superior fuel economy, acceleration and efficiency advantages, and deposit control. Surface modifiers are a way to improve efficiency by modifying engine surfaces to provide wear protection and / or reduce the coefficient of friction. Surface modifier components (also known as surfactants or surface-active substances) have both hydrophilic and lipophilic groups, which allows the component to be attracted to metal surfaces while remaining soluble in hydrocarbon environments.

[0003] Besides the polar and nonpolar heads of the surface modifier molecules, the self-arrangement of these molecules on the metal surface, enabling them to form a protective chemical wall, is also crucial. Molecular weight, stereochemical structure, and polar groups all work together to enhance the efficiency of the molecular protective properties. If the alkyl chain changes or side chains are present, preventing the molecules from packing tightly, or if the molecular weight is too low or sometimes too high, the protective efficiency will decrease sharply.

[0004] Alkyl succinates are known surface-modifying compounds. They are prepared by reacting alcohols with succinic anhydrides, producing isomers as shown below:

[0005]

[0006] US 3687644A relates to the use of alkyl succinates as anti-icing additives due to their chemical properties. Seung-Yeob Baek, "Synthesis of Succinic Acid Alkyl Half-Ester Derivatives with Improved Lubricity Characteristics", Ind. Eng. Chem. Res. 2012, 51, pp. 3564-3568, relates to the synthesis and use of alkyl succinates as diesel lubricants. However, none of these documents mention the use of alkyl succinate gasoline in reducing wear and friction, nor do they mention the use of alkyl succinate blends.

[0007] US2009 / 235576A1 relates to alkyl succinic acid and its derivatives as gasoline friction modifiers. However, this document does not mention the use of alkenyl succinate blends.

[0008] It has now been surprisingly discovered that the use of specific combinations of alkenyl succinate components in liquid fuel compositions can synergistically reduce engine wear. Summary of the Invention

[0009] According to the present invention, a fuel composition is provided comprising:

[0010] (i) a base fuel suitable for internal combustion engines; and

[0011] (ii) A blend of a first monoalkyl alkenyl succinate and a second monoalkyl alkenyl succinate, wherein the first monoalkyl alkenyl succinate and the second monoalkyl alkenyl succinate each have a formula (I) or (II) below, or a mixture of isomers of formulas (I) and (II) below:

[0012]

[0013] Where R is a straight-chain or branched alkenyl group containing 4 to 30 carbon atoms, and R 1 It is a straight-chain or branched C1 to C8 alkyl group;

[0014] Furthermore, the first monoalkyl alkenyl succinate is different from the second monoalkyl alkenyl succinate.

[0015] Surprisingly, the fuel composition of the present invention can synergistically reduce engine wear.

[0016] According to another aspect of the invention, a method for synergistically reducing engine wear in an internal combustion engine is provided, the method comprising supplying fuel to the internal combustion engine with a liquid fuel composition described herein below.

[0017] According to another aspect of the invention, there is provided the use of a liquid fuel composition as described herein for synergistically reducing engine wear. Attached Figure Description

[0018] Figure 1 This is a graphical representation of the data shown in Table 3 below.

[0019] Figure 2 This is a graphical representation of the data shown in Table 4 below.

[0020] Figure 3 This is a graphical representation of the data shown in Table 5 below. Detailed Implementation

[0021] To aid in understanding this invention, several terms are defined herein.

[0022] The fuel composition of the present invention comprises a base fuel and a blend of at least two monoalkyl alkenyl succinates.

[0023] The fuel compositions of the present invention synergistically reduce engine wear. As used herein, the term 'synergistically reduces engine wear' means that the reduction in engine wear obtained with the fuel compositions of the present invention comprising a blend of a first monoalkyl alkenyl succinate and a second monoalkyl alkenyl succinate as described herein is greater than the simple sum of the reduction in engine wear obtained with similar fuel formulations containing only the first monoalkyl alkenyl succinate (i.e., without the second monoalkyl alkenyl succinate) and the reduction in engine wear obtained with similar fuel formulations containing only the second monoalkyl alkenyl succinate (i.e., without the first monoalkyl alkenyl succinate). In other words, the reduction in engine wear obtained by the compositions, uses, and methods of the present invention is synergistic rather than additive.

[0024] In the context of this invention, the term "reduction in engine wear" 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 especially 2% or more, and even more especially 5% or more, of the reduction in engine wear obtained by the simple sum of the reduction in engine wear obtained by the similar fuel formulation containing only the first monoalkyl alkenyl succinate (i.e., without the second monoalkyl alkenyl succinate) and the reduction in engine wear obtained by the similar fuel formulation containing only the second monoalkyl alkenyl succinate (i.e., without the first monoalkyl alkenyl succinate). The reduction in engine wear can even be 20% higher than the reduction in engine wear obtained by the simple sum of the reduction in engine wear obtained by the similar fuel formulation containing only the first monoalkyl alkenyl succinate (i.e., without the second monoalkyl alkenyl succinate) and the reduction in engine wear obtained by the similar fuel formulation containing only the second monoalkyl alkenyl succinate (i.e., without the first monoalkyl alkenyl succinate).

[0025] Engine wear can be measured using any suitable method known in the art. A preferred method for measuring the effect of fuel composition on engine wear reduction is to use a high-frequency reciprocating test bench (HFRR), according to a modified version of ASTM D6079, using a gasoline conversion kit available from PCS Instruments (London, UK). The modified test uses a covered sample cup to prevent evaporation. The sample volume is 15 mL, and the sample temperature is maintained at 25°C. Film coverage is measured on a quartz crystal microbalance (QCM). In this method, the wear track diameter (μm) exhibited by the fuel composition is measured. The lower the wear track diameter value, the better the wear resistance of the tested fuel composition. Further details of the modified HFRR test method described above can be found in ‘In-Depth Analysis of Additive-Treated Gasoline with a Modified HFRR Technique’, Wendy Lang, Edward Malisa, Joseph Russo, Andreas Galwar, John Mengwasser, William Colucci, Kristine Morel, and Edward Nelson, SAE Int. J. Fuels Lubr., Vol. 13, No. 1, 2020. This method is also disclosed in US-A-10308889.

[0026] The liquid fuel composition of the present invention comprises a base fuel suitable for an internal combustion engine and a blend of monoalkyl alkenyl succinates comprising a first monoalkyl alkenyl succinate and a second monoalkyl alkenyl succinate, wherein the first monoalkyl alkenyl succinate and the second monoalkyl alkenyl succinate each have a formula (I) or (II) or a mixture of isomers of formulas (I) and (II):

[0027]

[0028]

[0029] Where R is a straight-chain or branched alkenyl group containing 4 to 30 carbon atoms, and R 1 It is a straight-chain or branched C1 to C8 alkyl group.

[0030] Importantly, the first monoalkyl alkenyl succinate is different from the second monoalkyl alkenyl succinate.

[0031] In formulas (I) and (II) above, the R group is an unsaturated hydrocarbon group attached to the ring; this is achieved through the alkylation of maleic anhydride with an alkene. Once the alkene reacts, the existing double bond moves from the α-β position in the alkene to the β-γ position in the alkylated succinic anhydride. Therefore, there is unsaturation in the R group, and the R group is a so-called alkenyl group.

[0032] In formulas (I) and (II) above, the R1 group is an alkyl group.

[0033] In one embodiment, the first monoalkyl alkenyl succinate is a compound of formula (I) or (II) or a mixture of isomers of formulas (I) and (II), wherein R is a straight-chain or branched alkenyl group containing 4 to 8 carbon atoms, and R 1 It is a C1 to C4 straight-chain or branched alkyl group.

[0034] In a preferred embodiment, the first monoalkyl alkenyl succinate is a compound of formula (I) or (II) or a mixture of isomers of formulas (I) and (II), wherein R is a straight-chain or branched alkenyl group containing 6 to 8 carbon atoms, and R 1 It is a straight-chain or branched C1 to C3 alkyl group.

[0035] In a particularly preferred embodiment, the first monoalkyl alkenyl succinate is a compound of formula (I) or (II) or a mixture of isomers of formulas (I) and (II), wherein R is a straight-chain alkenyl group containing 8 carbon atoms (i.e., octenyl), and R 1 Selected from methyl, ethyl, and isopropyl, preferably methyl and isopropyl.

[0036] In one embodiment, the second monoalkyl alkenyl succinate is a compound of formula (I) or (II) or a mixture of isomers of formulas (I) and (II), wherein R is a straight-chain or branched alkenyl group containing 10 to 22 carbon atoms, and R 1 It is a straight-chain or branched C1 to C6 alkyl group.

[0037] In a preferred embodiment, the second monoalkyl alkenyl succinate is a compound of formula (I) or (II) or a mixture of isomers of formulas (I) and (II), wherein R is a straight-chain or branched alkenyl group containing 12 to 18 carbon atoms, and R 1 It is a straight-chain or branched C1 to C6 alkyl group.

[0038] In a particularly preferred embodiment, the second monoalkyl alkenyl succinate is a compound of formula (I) or (II) or a mixture of isomers of formulas (I) and (II), wherein R is a straight-chain alkenyl group containing 12 to 18 carbon atoms, and R 1 It is selected from methyl, ethyl, isopropyl, pentyl and hexyl, preferably methyl, isopropyl and hexyl.

[0039] In a preferred embodiment herein, the R group in the first monoalkyl alkenyl succinate is different from the R group in the second monoalkyl alkenyl succinate. In particular, it is preferred that the R group in the second monoalkyl alkenyl succinate is longer than the R group in the first monoalkyl alkenyl succinate.

[0040] In a preferred embodiment of this document, when the R group in the first monoalkyl alkenyl succinate is C8 octenyl, the R group in the second monoalkyl alkenyl succinate is not C8 octenyl.

[0041] Preferred monoalkyl alkenyl succinates used as the first monoalkyl alkenyl succinate in this document are selected from monomethyl octenyl succinate and monoisopropyl octenyl succinate.

[0042] Preferred monoalkyl alkenyl succinates used as the second monoalkyl alkenyl succinate herein are selected from monohexyl C16C18 succinate (where C16C18 means a mixture of alkenyl groups containing 16 and 18 carbon atoms), monomethyl octadecenyl succinate, and monohexyl dodecenyl succinate.

[0043] Preferred blends of monoalkyl alkenyl succinates used herein (especially from the perspective of synergistic wear reduction) comprise:

[0044] Monomethyl octenyl succinate and monohexyl C16C18 succinate;

[0045] Monomethyl octenyl succinate and monomethyl octadecenyl succinate; and

[0046] Monoisopropyl octenyl succinate and monohexyl dodecenyl succinate.

[0047] Preferably, the total amount of the first monoalkyl alkenyl succinate and the second monoalkyl alkenyl succinate, based on the weight of the fuel composition, is in the range of 2 PTB to 262.3 PTB (1000 ppmw), preferably 3 PTB to 100 PTB, and more preferably 3.6 PTB to 14 PTB.

[0048] Preferably, the amount of the first monoalkyl alkenyl succinate, based on the weight of the fuel composition, is in the range of 1 PTB to 131.2 PTB (500 ppmw), more preferably 1.5 PTB to 50 PTB, and even more preferably 1.8 PTB to 7 PTB.

[0049] Preferably, the amount of the second monoalkyl alkenyl succinate, based on the weight of the fuel composition, is in the range of 1 PTB to 131.2 PTB (500 ppmw), more preferably 1.5 PTB to 50 PTB, and even more preferably 1.8 PTB to 7 PTB.

[0050] In a preferred embodiment, the weight ratio of the first monoalkyl alkenyl succinate to the second monoalkyl alkenyl succinate is in the range of 90:10 to 10:90, more preferably 80:20 to 20:80, even more preferably 70:30 to 30:70, and especially 50:50.

[0051] In a preferred embodiment of the invention, the blend of monoalkyl alkenyl succinates contains two monoalkyl alkenyl succinates, namely a first monoalkyl alkenyl succinate and a second monoalkyl alkenyl succinate. However, blends of monoalkyl alkenyl succinates that also contain one or more other monoalkyl alkenyl succinates in addition to the first and second alkenyl succinates are also within the scope of the invention.

[0052] Monoalkyl alkenyl succinates can be prepared by reacting alkenyl succinic anhydride with the corresponding alcohol using standard techniques known in the art.

[0053] Blends of monoalkyl alkenyl succinates can be blended with any other additives (e.g., additive performance packages) to prepare additive blends. The additive blends are then added to a base fuel to prepare a liquid fuel composition.

[0054] The amount of the performance package in the additive blend is preferably in the range of 0.1% to 99.8% by weight, more preferably in the range of 5% to 50% by weight, based on the weight of the additive blend.

[0055] Preferably, based on the total weight of the liquid fuel composition, the amount of performance packets present in the liquid fuel composition of the present invention is in the range of 15 ppmw (parts per million by weight) to 10% by weight. More preferably, the amount of performance packets present in the liquid fuel composition of the present invention further meets one or more of the following parameters (i) to (XV):

[0056] (i) at least 100 ppmw

[0057] (ii) at least 200 ppmw

[0058] (iii) At least 300 ppmw

[0059] (iv) at least 400 ppmw

[0060] (v) at least 500 ppmw

[0061] (vi) At least 600 ppmw

[0062] (vii) At least 700 ppmw

[0063] (viii) At least 800 ppmw

[0064] (ix) at least 900 ppmw

[0065] (x) at least 1000 ppmw

[0066] (xi) at least 2500ppmw

[0067] (xii) up to 5000ppmw

[0068] (xiii) Up to 10,000 ppmw

[0069] (xiv) up to 2wt%.

[0070] (xv) up to 5wt%.

[0071] The base fuel suitable for internal combustion engines can be gasoline or diesel fuel, and therefore the liquid fuel compositions of the present invention are either gasoline compositions or diesel fuel compositions. In the fuel compositions herein, the base fuel is preferably gasoline.

[0072] 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 be conveniently referred to as 'base gasoline'.

[0073] 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.

[0074] The specific distillation profile, hydrocarbon composition, research octane number (RON), and motor octane number (MON) of gasoline are not critical.

[0075] Conveniently, the research octane number (RON) of the gasoline may 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 (EN 25164); the motor octane number (MON) of the gasoline may 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; and most preferably, the MON of the gasoline will be at least 82, for example, in the range of 82 to 95 (EN 25164). 25163).

[0076] 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.

[0077] Typically, the olefin content of gasoline is in the range of 0% to 40% by volume based on gasoline (ASTM D1319); preferably, the olefin content of gasoline is in the range of 0% to 30% by volume based on gasoline; more preferably, the olefin content of gasoline is in the range of 0% to 20% by volume based on gasoline.

[0078] Typically, the aromatic content of gasoline is in the range of 0% to 70% by volume (ASTM D1319), for example, the aromatic content of gasoline is in the range of 10% to 60% by volume; preferably, the aromatic content of gasoline is in the range of 0% to 50% by volume, for example, the aromatic content of gasoline is in the range of 10% to 50% by volume.

[0079] In one embodiment of this document, the gasoline base fuel contains less than 10% by volume of aromatic compounds based on total base fuel. In another embodiment of this document, the gasoline base fuel contains less than 2% by volume of aromatic compounds having nine or more carbon atoms based on total base fuel.

[0080] 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.

[0081] 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.

[0082] 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).

[0083] When gasoline contains oxidized hydrocarbons, at least a portion of the non-oxidized hydrocarbons will replace the oxidized hydrocarbons (matching blend) or simply be added to the fully formulated gasoline (splash blend). Based on gasoline content, the oxygenated compound content of the gasoline can be up to 85% by weight (EN 1601) (e.g., ethanol itself). For example, the oxygenated compound content of the gasoline can be up to 35% by weight, preferably up to 25% by weight, more preferably up to 10% by weight. Conveniently, the oxygenated compound concentration 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 12% by weight, 8% by weight, 7.2% by weight, 5% by weight, 4.5% by weight, 4.0% by weight, 3.5% by weight, 3.0% by weight, and 2.7% by weight.

[0084] Examples of oxidized hydrocarbons that can be blended into gasoline include alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, as well as oxygen-containing heterocyclic compounds. Preferably, the oxidized hydrocarbons that can be blended 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.

[0085] 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.

[0086] Examples of suitable gasoline include gasoline with an olefin content of 0% to 20% by volume (ASTM D1319), an oxygen content of 0% to 5% by weight (EN 1601), an aromatic content of 0% to 50% by volume (ASTM D1319), and a benzene content of up to 1% by volume.

[0087] Also applicable here are gasoline blends, which can be derived from sources other than crude oil, such as low-carbon gasoline fuels from biomass or CO2, and blends of these with each other or with gasoline streams and components from fossil sources. Suitable examples of such fuels include:

[0088] 1) Biomass-derived:

[0089] a. Straight-run bio-naphtha derived from biomass through hydrodeoxygenation, and

[0090] b. The cracking and / or isomerization products of synthetic wax (biomass gasification into syngas (CO / H2), which is then converted into synthetic wax via an FT process), are then hydrocracking / hydroisomerized to produce a series of products including fractions within the gasoline range.

[0091] 2) Sources of CO2:

[0092] a. CO2 + H2 syngas (CO / H2) (to synthetic wax via a modified water / gas shift reaction and FT process), which is then hydrocracking / hydroisomerized to produce a series of products including fractions within the gasoline range.

[0093] 3) Methanol source:

[0094] a. Biomass is gasified into syngas (CO / H2), then into methanol, and finally into MTG gasoline (MTG is the "methanol-gasoline" process). To further reduce the carbon intensity of the fuel, the H2 used in all processes will be renewable (green) H2 derived from water electrolysis using renewable electricity (such as from wind and solar power).

[0095] Particularly 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.

[0096] Although not critical to the present invention, the base gasoline or gasoline composition of the present invention may conveniently include one or more optional fuel additives in addition to the basic blends of the monoalkyl alkenyl succinates described above. 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, detergents, defoggers, antiknock additives, metal deactivators, valve seat depression protectant compounds, dyes, solvents, carrier fluids, diluents, and markers. Examples of suitable such additives are generally described, for example, in U.S. Patent No. 5,855,629.

[0097] 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.

[0098] 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 ppmw to 2000 ppmw, advantageously in the range of 300 ppmw to 1500 ppmw, such as 300 ppmw to 1000 ppmw.

[0099] As mentioned above, the gasoline composition may also contain synthetic or mineral carrier oils and / or solvents.

[0100] Examples of suitable mineral carrier oils are fractions obtained from crude oil processing, such as bright oils or base oils with viscosity grades of, for example, SN 500-2000; and aromatics, alkanes, and alkoxyalkanols. Also suitable as mineral carrier oils are fractions obtained from mineral oil refining, and are referred to as "hydrocracked oils" (vacuum fractions with boiling points ranging from about 360°C to 500°C, obtained from natural mineral oils through catalytic hydrogenation, isomerization, and dewaxing under high pressure).

[0101] Examples of suitable synthetic carrier oils are: polyolefins (poly-α-olefins or poly(inner olefins)), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-based polyethers, alkylphenol-based polyetheramines, and carboxylic acid esters of long-chain alkanols.

[0102] Suitable examples of polyolefins are olefin polymers, particularly olefin polymers based on polybutene or polyisobutylene (hydrogenated or non-hydrogenated).

[0103] Suitable examples of polyethers or polyetheramines are preferably compounds containing a polyoxy-C2-C4-alkylene moiety, which can be produced by making the C2-C4-alkylene moiety... 60 -Alkanols, C6-C 30 -Alkanediol, mono- or di-C2-C30 -alkylamines, C1-C 30 -alkylcyclohexanol or C1-C 30 - Alkylphenols are obtained by reacting 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butene oxide per hydroxyl or amino group, and in the case of polyetheramines, by subsequent reductive amination with ammonia, a monoamine, or a polyamine. Such products are specifically described in EP-A-310 875, EP-A-356 725, EP-A-700 985, and US-A-4,877,416. For example, the polyetheramine used can be a poly-C2-C6-oxyenamine or a functional derivative thereof. Typical examples are tridecyl alcohol butoxylates or isotridel alcohol butoxylates, isononylphenol butoxylates, and polyisobutylene alcohol butoxylates and propoxylates, and their corresponding reaction products with ammonia.

[0104] Examples of carboxylic acid esters of long-chain alkanols are particularly esters of mono-, di-, or tricarboxylic acids with long-chain alkanols or polyols, especially as described in DE-A-38 38 918. The mono-, di-, or tricarboxylic acids used can be aliphatic or aromatic acids; suitable ester alcohols or polyols are particularly long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of esters are adipates, phthalates, isophthalates, terephthalates, and trimellites of isooctanol, isononanol, isodecanol, and isotrimethylenetetramine, such as di(n-tetrazyl or isotrimethylenetetramine) phthalates.

[0105] Other suitable carrier oil systems are described in, for example, DE-A-38 26 608, DE-A-41 42 241, DE-A-4309 074, EP-A-0 452 328 and EP-A-0 548 617, which are incorporated herein by reference.

[0106] Particularly suitable examples of synthetic carrier oils are polyethers starting with alcohols having about 5 to 35, for example about 5 to 30, C3-C6-olefin oxide units, such as those selected from propylene oxide, n-butene oxide, and isobutene oxide units, or mixtures thereof. Non-limiting examples of suitable starting alcohols are long-chain alkanols or phenols substituted with long-chain alkyl groups, wherein the long-chain alkyl groups are particularly straight-chain or branched C6-C18-alkyl groups. Preferred examples include tridecyl alcohol and nonylphenol.

[0107] Other suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A-10 102 913.6.

[0108] Mineral carrier oils, synthetic carrier oils, and mixtures of mineral and synthetic carrier oils can also be used.

[0109] Any solvent suitable for the fuel and optional co-solvents may be used. Examples of suitable solvents for the fuel include: nonpolar hydrocarbon solvents such as kerosene, heavy aromatic solvents (“solvent oil heavy”, “Solvesso 150”), toluene, xylene, paraffin, petroleum, petroleum solvents (white spirits), and those sold by Shell companies under the trade name “SHELLSOL”, etc. Examples of suitable co-solvents include: polar solvents, such as esters, and especially alcohols (e.g., tert-butanol, isobutanol, hexanol, 2-ethylhexanol, 2-propylheptanol, decanol, isotretinoin, butyl glycol, and mixtures of alcohols, such as those sold by Shell companies under the trademark “LINEVOL”, especially LINEVOL 79 alcohol, which is C 7-9 A mixture of primary alcohols, or C 12-14 (A mixture of alcohols, which is commercially available).

[0110] Demisters / demulsifiers suitable for liquid fuels are well known in the art. Non-limiting examples include blends of diol alkoxylated polyols (such as those marketed under the trade name TOLAD). TM 9312 for sale), alkoxylated phenol-formaldehyde polymer, through the use of C 1-18 Epoxide and diepoxide alkoxylation modified phenol / formaldehyde or C 1-18 Alkylphenol / formaldehyde resin alkoxylates (such as those marketed under the trade name TOLAD) TM 9308 (for sale), and C crosslinked with diepoxides, diacids, diesters, glycols, diacrylates, dimethacrylates, or diisocyanates. 1-4 Epoxide copolymers and their blends. Diol alkoxylated polyol blends can be made using C 1-4 Epoxide-alkoxylated polyols. Through the use of C... 1-18 Epoxide and diepoxide alkoxylation modified C 1-18 Alkylphenol / formaldehyde resin alkoxylates may be based on, for example, cresol, tert-butylphenol, dodecylphenol, or dinonylphenol, or mixtures of phenols (such as mixtures of tert-butylphenol and nonylphenol). The amount of defogging agent used should be sufficient to suppress fogging that may occur when gasoline without defogging agent comes into contact with water, and this amount is referred to herein as the "fogging suppression amount". Typically, based on the weight of gasoline, this amount is from about 0.1 ppmw to about 20 ppmw (e.g., from about 0.1 ppm to about 10 ppm), more preferably from 1 ppmw to 15 ppmw, even more preferably from 1 ppmw to 10 ppmw, advantageously from 1 ppmw to 5 ppmw.

[0111] Other conventional additives used in gasoline include corrosion inhibitors, such as ammonium salts based on organic carboxylic acids, which tend to form a film, or ammonium salts based on heterocyclic aromatic hydrocarbons used for nonferrous metal corrosion protection; antioxidants or stabilizers, such as those based on amines like phenylenediamine, such as p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, dicyclohexylamine or derivatives thereof, or those based on phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; antistatic agents; metallocenes such as ferrocene; methyl-cyclopentadienyl manganese tricarbonyl; lubricating additives such as certain fatty acids, alkenyl succinates, bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; and dyes (markers). Amines, such as those described in WO 03 / 076554, may also be added if appropriate. Optionally, anti-seat sink-in additives, such as sodium or potassium salts of polymeric organic acids, may be used.

[0112] In addition to the above-described blends of monoalkyl alkenyl succinates, the gasoline compositions herein may also contain detergent additives. Suitable detergent additives include those disclosed in WO2009 / 50287, which is incorporated herein by reference.

[0113] Preferred detergent additives used in the gasoline compositions herein typically have at least one hydrophobic hydrocarbon group with a number-average molecular weight (Mn) of 85 to 20,000 and at least one polar moiety selected from:

[0114] (A1) A monoamino or polyamino group having up to 6 nitrogen atoms, wherein at least one nitrogen atom is basic;

[0115] (A6) Polyoxy-C2- to -C4-alkylene groups, which are capped by hydroxyl, monoamino or polyamino groups, wherein at least one nitrogen atom is basic, or are capped by urethane groups;

[0116] (A8) A moiety derived from succinic anhydride and having hydroxyl and / or amino and / or amide and / or imide groups; and / or

[0117] (A9) The portion obtained by the Mannich reaction of substituted phenols with aldehydes and monoamines or polyamines.

[0118] The hydrophobic hydrocarbon groups in the aforementioned cleaning additives that ensure sufficient solubility in the base fluid have a number average molecular weight (Mn) of 85 to 20,000, particularly 113 to 10,000, and especially 300 to 5,000. Typical hydrophobic hydrocarbon groups, especially those bonded to the polar moieties (A1), (A8), and (A9), include polyolefins, such as polypropylene, polybutene, and polyisobutylene, each having a Mn of 300 to 5,000, preferably 500 to 2,500, more preferably 700 to 2,300, and especially 700 to 1,000.

[0119] Non-limiting examples of the above-mentioned cleaning additive group include the following:

[0120] 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.

[0121] Other preferred additives containing a single amino group (A1) are hydrogenated products of the reaction of polyisobutylene with nitrogen oxides or mixtures of nitrogen oxides and oxygen with an average degree of polymerization of 5 to 100, particularly as described in WO-A-97 / 03946.

[0122] Other preferred additives containing a single amino group (A1) are compounds that can be obtained from polyisobutylene epoxides by reacting with an amine and subsequently dehydrating and reducing the amino alcohol, particularly as described in DE-A-19620262.

[0123] Additives containing polyoxy-C2-C4-alkylene moieties (A6) are preferably polyethers or polyether amines, which can be converted from C2- to C4-alkylene moieties. 60 -Alkanols, C6-to-C 30 -Alkanediol, mono- or di-C2-C 30 -alkylamines, C1-C 30 -alkylcyclohexanol or C1-C 30- Alkylphenols are obtained by reacting 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butene oxide per hydroxyl or amino group, and in the case of polyether amines, by subsequent reductive amination with ammonia, a monoamine, or a polyamine. Such products are specifically described in EP-A-310875, EP-A-356725, EP-A-700985, and US-A-4877416. In the case of polyethers, such products also exhibit carrier oil properties. Typical examples of these products are tridecaneol butoxylates, isotriadecaneol butoxylates, isononylphenol butoxylates, and polyisobutylene butoxylates and propoxylates, as well as their corresponding reaction products with ammonia.

[0124] Additives comprising a moiety (A8) derived from succinic anhydride and having hydroxyl and / or amino and / or amide and / or imide groups are preferably corresponding derivatives of polyisobutylene-succinic anhydride, which can be obtained by reacting conventional or highly reactive polyisobutylene with a Mn of 300 to 5000 with maleic anhydride via a thermal route or via chlorinated polyisobutylene. Of particular interest are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine. Such additives are specifically described in US-A-4 849 572.

[0125] Additives containing a portion (A9) obtained by the Mannich reaction of a substituted phenol with an aldehyde and a monoamine or polyamine are preferably reaction products of polyisobutylene-substituted phenols with formaldehyde and monoamines or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or dimethylaminopropylamine. The polyisobutylene-substituted phenol can be derived from conventional or highly reactive polyisobutylene with a Mn of 300 to 5000. Such “polyisobutylene-Mannich bases” are specifically described in EP-A-831 141.

[0126] Preferably, the detergent additive used in the gasoline composition of the present invention contains at least one nitrogen-containing detergent, more preferably at least one nitrogen-containing detergent containing a hydrophobic hydrocarbon group with a number average molecular weight in the range of 300 to 5000. Preferably, the nitrogen-containing detergent is selected from the group consisting of: polyolefin monoamines, polyetheramines, polyolefin Mannich amines, and polyolefin succinimides. Conveniently, the nitrogen-containing detergent may be a polyolefin monoamine.

[0127] In the above text, the amount of components (concentration, volume %, ppmw, weight %) refers to the amount of active material, excluding volatile solvent / diluent materials.

[0128] The liquid fuel compositions of the present invention can be prepared by mixing a blend of monoalkyl alkenyl succinates with a gasoline base fuel suitable for internal combustion engines (and optionally any other additive components).

[0129] 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.

[0130] Example

[0131] The purpose of these experiments was to screen a group of monoalkyl alkenyl succinate blends for engine wear characteristics.

[0132] Preparation of monoalkyl alkenyl succinates

[0133] The monoalkyl alkenyl succinates used in these examples were prepared as follows. Toluene was added to a three-necked round-bottom flask equipped with a heating mantle, glass stir bar, thermometer, reflux condenser, inert dry nitrogen, and dropping funnel, followed by the relevant acid anhydride. The relevant alcohol was then added to the dropping funnel, and the mixture was heated to 50°C-60°C while stirring. Methanol was then slowly added via the dropping funnel to prepare the methyl ester. When using other alcohols, the reactor temperature was increased from 70°C to 80°C while higher chain alcohols were slowly added via the dropping funnel. The total reaction time was 10 hours, after which the reactor was allowed to cool overnight to room temperature. Some of the corresponding esters were monitored by C13 NMR to determine if the correct temperature, addition rate, and total reaction length were optimal. Additionally, C13 NMR confirmed the two expected isomers and the major and minor chemical structures. The reactions producing the corresponding major and minor components can be seen below:

[0134]

[0135] C13 NMR analysis of the fifteen synthesized alkyl succinates showed 100% complete reaction. A slight excess of alcohol remained, and the remaining amount of alkyl succinic anhydride was zero.

[0136] Table 1 below lists the alkenyl succinate anhydrides and alcohols used to prepare the alkenyl succinate anhydrides used in this paper, as well as the molecular weights of the starting materials and the molecular weights and yields of the products. Table 2 below illustrates the C13 NMR analyses of the fifteen alkyl succinates prepared.

[0137] Gasoline fuel compositions were prepared by blending one or two of the alkenyl succinates prepared above with a standard additive package, and then adding the resulting mixture to a reference fuel (E10 base fuel (a gasoline base fuel containing 10% by volume ethanol)). The standard gasoline additive package was identical in each fuel composition and contained detergents (except for the alkenyl succinates), a demisting agent, a carrier fluid, and a solvent. The amount of the standard gasoline additive package in all fuel compositions was 172.8 PTB. The amounts and combinations of monoalkyl alkenyl succinates used in the fuel compositions are illustrated in Tables 3-5 below.

[0138] Wear measurements for each fuel composition described in Tables 3-5 were performed using a high-frequency reciprocating test bench (HFRR) according to a modified version of ASTM D6079, using a gasoline conversion kit available from PCR Instruments (London, UK). The procedure using the HFRR and gasoline conversion kit is provided in "The Lubricity of Gasoline", DPWei, H.A. Spikes & S. Koreck, Tribology Transactions, 42: 4813-823 (1999), which is incorporated herein by reference. Wear data are shown in Tables 3-5 below.

[0139] Figure 1 This is a graphical representation of the data described in Table 3.

[0140] Figure 2 This is a graphical representation of the data described in Table 4.

[0141] Figure 3 This is a graphical representation of the data described in Table 5.

[0142] Table 1

[0143]

[0144]

[0145] 1. Alkenyl succinic anhydride containing a mixture of C16 and C18 alkyl chains

[0146] 2. Molecular weight

[0147] Table 2: NMR C13 analysis of fifteen alkyl succinates

[0148]

[0149]

[0150]

[0151] 1. A = Major product, B = Minor product, S = Initial anhydride 2. NM = Not measured

[0152] Table 3

[0153]

[0154]

[0155] Table 4

[0156]

[0157] Table 5

[0158]

[0159] discuss

[0160] Table 3-5 and Figures 1 to 3 The data contained herein demonstrates that blending specific monoalkyl alkenyl succinates together results in abrasion reduction in the blend exceeding the synergistic effect of the individual components. Individual alkyl succinate components may not be able to predict or achieve this synergistic beneficial effect on abrasion resistance.

Claims

1. A fuel composition comprising: (i) a base fuel suitable for internal combustion engines, wherein the base fuel is a gasoline base fuel; and (ii) A blend of a first monoalkyl alkenyl succinate and a second monoalkyl alkenyl succinate, wherein the first monoalkyl alkenyl succinate is a compound of formula (I) or (II) or a mixture of isomers of formulas (I) and (II), wherein R is a straight-chain or branched alkenyl group containing 4 to 8 carbon atoms, and R 1 It is a straight-chain or branched C1 to C4 alkyl group; and the second monoalkyl alkenyl succinate is a compound of formula (I) or (II) or a mixture of isomers of formula (I) and (II), wherein R is a straight-chain or branched alkenyl group containing 10 to 22 carbon atoms, and R 1 It is a straight-chain or branched C1 to C6 alkyl group; Furthermore, the first monoalkyl alkenyl succinate is different from the second monoalkyl alkenyl succinate. The weight ratio of the first monoalkyl alkenyl succinate to the second monoalkyl alkenyl succinate is in the range of 90:10 to 10:

90.

2. The fuel composition according to claim 1, wherein the fuel composition is a gasoline fuel composition.

3. The fuel composition according to claim 1 or 2, wherein the first monoalkyl alkenyl succinate is a compound of formula (I) or (II) or a mixture of isomers of formulas (I) and (II), wherein R is a straight-chain or branched alkenyl group containing 6 to 8 carbon atoms, and R 1 It is a straight-chain or branched C1 to C3 alkyl group.

4. The fuel composition according to claim 1 or 2, wherein the second monoalkyl alkenyl succinate is a compound of formula (I), wherein R is a straight-chain or branched alkenyl group containing 12 to 18 carbon atoms, and R 1 It is a straight-chain or branched C1 to C6 alkyl group.

5. The fuel composition according to claim 1 or 2, wherein the total amount of the first monoalkyl alkenyl succinate and the second monoalkyl alkenyl succinate, based on the weight of the fuel composition, is in the range of 2 PTB to 262.3 PTB.

6. Use of the fuel composition according to any one of claims 1 to 5 for providing synergistically reduced engine wear.

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