JP2011529517A - Liquid fuel composition - Google Patents

Abstract

The present invention includes a suitable base fuel for use in internal combustion engines, the formula _{(III): [Y-CO} [O-A-CO] n -Z p] m -X (III) ( wherein, Y is hydrogen Or an optionally substituted hydrocarbyl group, A is a divalent optionally substituted hydrocarbyl group, n is 1 to 100, m is 1 or 2, and Z is optionally substituted. A divalent bridging group, p is 0 or 1, and X is a group having a terminal acid group or a terminal acid group selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate A liquid fuel composition comprising one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups.
[Selection figure] None

Description

  The present invention relates to a liquid fuel composition comprising a major amount of base fuel suitable for use in an internal combustion engine, and more particularly to a liquid fuel composition comprising a major amount of base fuel suitable for use in an internal combustion engine and a superdispersant. .

  EP-A-0164817 A2 is selected from carboxylic acids, carboxymethyl, sulfates, sulfonates, phosphates and phosphonates suitable for stabilizing solid dispersions and oil / water emulsions in organic liquids. Surfactants containing carboxylic esters or amides having strong terminal acid groups are disclosed. A preferred type of surfactant is a poly (hydroxyalkanecarboxylic acid) having a strong acid group attached to the terminal hydroxy or carboxylic acid group, either directly or via a linking group. The use of such surfactants in fuels is not disclosed in that specification.

  EP-A-0233684 A1 is suitable for use as a dispersant for solids in organic liquids (i) end groups containing at least two aliphatic carbon-carbon double bonds; (Ii) An ester or polyester having an acidic or basic amino group is disclosed. The use of such surfactants in fuels is not disclosed in that specification.

GB-A-219731 A first reacts a C ₅ -C ₉ lactone with a polyamine, polyol or aminoalcohol to form an intermediate adduct, after which the intermediate adduct is from about 1 to about 165. Disclosed is an oil-soluble dispersant additive which is a poly (C ₅ -C ₉ lactone) adduct produced by reacting with an aliphatic hydrocarbyl monocarboxylic acid or dicarboxylic acylating agent having a total number of carbon atoms. ing. The use of this dispersant additive in lubricants and fuels is also disclosed in GB-A-2 197 312 A.

  EP-A-0802255 A2 discloses hydroxyl group-containing acylated nitrogen compounds that are useful as low chlorine-containing additives for lubricating oils and usually liquid fuels, and a process for the preparation of the compounds.

  WO 00/34418 A1 discloses the use of poly (hydroxycarboxylic acid) amide or ester derivatives in fuel compositions as lubricity additives. The use of the poly (hydroxycarboxylic acid) amide or ester derivatives disclosed in that specification also allows for inlet system cleanliness (intake valves, fuel injectors, carburetors), combustion chamber cleanliness (in each case maintaining cleanliness) (Keep clean effect and / or cleanliness improvement effect), anticorrosion (including rust prevention), and may result in one or more of a number of effects such as reduced or eliminated valve sticking Is also disclosed in WO 00/34418 A1.

  It has now been found that the use of poly (hydroxycarboxylic acid) derivatives having terminal acid groups can also surprisingly provide benefits in terms of improving the lubricity of liquid fuel compositions incorporating them.

The present invention
-A liquid based fuel suitable for use in an internal combustion engine;
-Formula (III):
_{[Y-CO [O-A} -CO] n -Z p] m -X (III)
Wherein Y is hydrogen or an optionally substituted hydrocarbyl group, A is a divalent optionally substituted hydrocarbyl group, n is 1 to 100, m is 1 or 2, Z is an optionally substituted divalent bridging group, p is 0 or 1, and X is a terminal acid group or terminal acid selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate It is a group that has a group)
One or more poly (hydroxycarboxylic acid) derivatives having terminal strong acid groups having:
A liquid fuel composition is provided.

  The present invention further provides a process for preparing the liquid fuel composition of the present invention comprising mixing one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups with a base fuel suitable for use in an internal combustion engine. To do.

  The present invention still further provides a method of operating an internal combustion engine comprising introducing the liquid fuel composition according to the present invention into the combustion chamber of the engine.

  The liquid fuel composition of the present invention comprises a base fuel suitable for use in an internal combustion engine and one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups. Generally, the base fuel suitable for use in an internal combustion engine is gasoline or diesel fuel, and therefore the liquid fuel composition of the present invention is generally a gasoline composition or a diesel fuel composition.

  The poly (hydroxycarboxylic acid) derivatives having terminal acid groups used in the present invention may also be referred to as superdispersants.

One or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups in the liquid fuel composition of the present invention are represented by the formula (III):
_{[Y-CO [O-A} -CO] n -Z p] m -X (III)
Wherein Y is hydrogen or an optionally substituted hydrocarbyl group, A is a divalent optionally substituted hydrocarbyl group, n is 1 to 100, m is 1 or 2, Z is an optionally substituted divalent bridging group, p is 0 or 1, and X is a terminal acid group or terminal selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate It is a group having an acid group)
It is a poly (hydroxycarboxylic acid) derivative having a terminal acid group.

  In formula (III), A is preferably a divalent linear or branched hydrocarbyl group as described herein below for formulas (I) and (II).

  That is, in formula (III), A is preferably an optionally substituted aromatic, aliphatic or alicyclic straight chain or branched divalent hydrocarbyl group. More preferably, A is an arylene, alkylene or alkenylene group, especially in the range of 4-25 carbon atoms, more preferably in the range of 6-25 carbon atoms, more preferably in the range of 8-24 carbon atoms. More preferably an arylene, alkylene or alkenylene group containing in the range of 10 to 22 carbon atoms, most preferably in the range of 12 to 20 carbon atoms.

  Preferably, in said compound of formula (III), at least 4 carbon atoms, more preferably at least 6 carbon atoms connected directly between the carbonyl group and the oxygen atom derived from the hydroxyl group, even more preferably Are present in the range of 8 to 14 carbon atoms.

In the compounds of formula (III), the optional substituents in group A are preferably selected from hydroxy, halo or alkoxy groups, especially C _1-4 alkoxy groups.

  In formula (III) (and formula (I)), n is in the range of 1-100. Preferably, the lower limit of the range for n is 1, more preferably 2, still more preferably 3; preferably the upper limit of the range for n is 100, more preferably 60, more preferably 40, more preferably 20 And even more preferably 10 (ie, n may be selected from any of the following ranges: 1-100; 2-100; 3-100; 1-60; 2-60; 3-60; 1-40; 2-40; 3-40; 1-20; 2-20; 3-20; 1-10; 2-10; and 3-10).

  In formula (III), Y is preferably a hydrocarbyl group optionally substituted as described hereinabove for formula (I).

  That is, the optionally substituted hydrocarbyl group Y in formula (III) is preferably aryl, alkyl or alkenyl containing up to 50 carbon atoms, more preferably in the range of 7 to 25 carbon atoms. For example, the optionally substituted hydrocarbyl group Y may conveniently be selected from heptyl, octyl, undecyl, lauryl, heptadecyl, heptadenyl, heptadecadienyl, stearyl, oleyl and linoleyl.

Other examples of said optionally substituted hydrocarbyl group Y in formula (III) herein include C _4-8 cycloalkyl such as cyclohexyl; polycycles derived from naturally occurring acids such as abietic acid Polycycloalkyls of the formula terpenyl group; aryls such as phenyl; aralkyls such as benzyl; and polyaryls such as naphthyl, biphenyl, stibenyl and phenylmethylphenyl.

  In the present invention, an optionally substituted hydrocarbyl group Y in formula (III) is a carbonyl, carboxyl, nitro, hydroxy, halo, alkoxy, amino, preferably a tertiary amino (no NH bond), oxy, It may contain one or more functional groups such as cyano, sulfonyl and sulfoxyl. Most of the atoms in the substituted hydrocarbyl group, other than hydrogen, are generally carbon, and heteroatoms (eg, oxygen, nitrogen and sulfur) account for a small portion of all non-hydrogen atoms present, up to about 33%. It's just a general representation.

A functional group such as hydroxy, halo, alkoxy, nitro and cyano in the substituted hydrocarbyl group Y replaces one of the hydrogen atoms of the hydrocarbyl, but carbonyl, carboxyl, tertiary amino (—N—), oxy in the substituted hydrocarbyl group. Those skilled in the art will appreciate that functional groups such as sulfonyl and sulfoxyl replace the —CH— or CH ₂ — moiety of hydrocarbyl.

More preferably, the hydrocarbyl group Y in formula (III) is unsubstituted or substituted with a group selected from hydroxy, halo or alkoxy groups, still more preferably C _1-4 alkoxy.

  Most preferably, the optionally substituted hydrocarbyl group Y in formula (III) is derived from naturally occurring oils such as stearyl groups, 12-hydroxystearyl groups, oleyl groups or 12-hydroxyoleyl groups, and tall oil fatty acids. To do.

In formula (III), Z is a divalent bridging group which is optionally substituted, preferably of the formula ^-X _z ^-B-Y z _q - is (wherein, ^{X z} oxygen, sulfur or, ^{R 1} is Selected from a group of formula —NR ¹ —, as described below, B is as described below, and Y ^z is oxygen or R ¹ is as described below, An optionally substituted divalent bridging group selected from the group of formula —NR ¹ — and q is 0 or 1. When q is 1 and both X ^z and Y ^z are groups of the formula —NR ¹ —, the two R ¹ groups may form a single hydrocarbyl group that connects two nitrogen atoms. .

Conveniently, Z is attached to the carbonyl group via a nitrogen atom, preferably of formula (IV)

(Wherein R ¹ is hydrogen or a hydrocarbyl group, and B is an optionally substituted alkylene group)
Is an optionally substituted divalent bridging group.

Examples of hydrocarbyl groups that may represent R ¹ include methyl, ethyl, n-propyl, n-butyl and octadecyl.

  Examples of optionally substituted alkylene groups that may represent B include ethylene, trimethylene, tetramethylene and hexamethylene.

Examples of preferred Z moieties in formula (III) include —NHCH ₂ CH ₂ —, —NHCH ₂ C (CH ₃ ) ₂ CH ₂ — and NH (CH ₂ ) ₃ —.

In formula (III), X is a group having a terminal acid group or a terminal acid group selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate. When X is a group having a terminal acid group, preferably it is -Z ¹ -X ^{1 where} Z ¹ is a polyamine, polyol, hydroxylamine, or a Z group as defined above. A bifunctional linking compound, such as a selected compound, wherein X ¹ is a terminal acid group selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate; , X is a group having a terminal acid group, p in the formula (III) is 0, and X is a group of the formula -Z ¹ -X ¹ .

The terminal acid group may be present in the free acid form or in the acid salt form. Where the terminal acid group is in the form of a salt, it can conveniently be formed by reaction of the free acid form of the terminal acid with a base, for example, organic bases such as ammonia, amines and aminoalcohols, and inorganic bases. it can. When the acid group at the terminal acid group is a salt, examples of suitable cations include metal ions such as sodium, potassium and calcium, ammonium ions (NH ₄ ⁺ ), N (CH ₃ ) ₄ ⁺ , and NH Examples include ammonium ions such as (CH ₃ ) ₄ ⁺ .

One or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups are represented by the formula (I)
Y-CO [O-A-CO] _n- OH (I)
Wherein Y is hydrogen or an optionally substituted hydrocarbyl group, A is a divalent optionally substituted hydrocarbyl group, and n is 1-100.
Of poly (hydroxycarboxylic acid)
A compound of the poly (hydroxycarboxylic acid) of formula (I) having a group which reacts with a carboxylic acid group and a terminal acid group selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate;
It may be obtained by reacting with a precursor of a terminal acid group; or a bifunctional linking compound that is subsequently reacted with a precursor of a terminal acid group.

  As used herein, the term “hydrocarbyl” refers to a radical formed by the removal of one or more hydrogen atoms from a hydrocarbon carbon atom (not necessarily when more hydrogen atoms are removed). Not the same carbon atoms).

  The hydrocarbyl group may be an aromatic, aliphatic, acyclic or cyclic group. Preferably, hydrocarbyl groups are aryl, cycloalkyl, alkyl or alkenyl, in which case they may be straight or branched chain groups.

  Representative hydrocarbyl groups include phenyl, naphthyl, methyl, ethyl, butyl, pentyl, methylpentyl, hexenyl, dimethylhexyl, octenyl, cyclooctenyl, methylcyclooctenyl, dimethylcyclooctyl, ethylhexyl, octyl, isooctyl, dodecyl, hexadecenyl , Eicosyl, hexacosyl, triacontyl and phenylethyl.

  In the present invention, the phrase “optionally substituted hydrocarbyl” is used to describe a hydrocarbyl group optionally containing one or more “inert” heteroatom-containing functional groups. “Inert” means that the functional group does not interfere with the function of the compound to any substantial extent.

  An optionally substituted hydrocarbyl group Y in formula (I) is preferably an aryl, alkyl or alkenyl containing not more than 50 carbon atoms, more preferably in the range of 7 to 25 carbon atoms herein. It is. For example, the optionally substituted hydrocarbyl group Y may conveniently be selected from heptyl, octyl, undecyl, lauryl, heptadecyl, heptadenyl, heptadecadienyl, stearyl, oleyl and linoleyl.

Other examples of said optionally substituted hydrocarbyl group Y in formula (I) herein include C _4-8 cycloalkyl such as cyclohexyl; polycycles derived from naturally occurring acids such as abietic acid Polycycloalkyls of the formula terpenyl group; aryls such as phenyl; aralkyls such as benzyl; and polyaryls such as naphthyl, biphenyl, stibenyl and phenylmethylphenyl.

  In the present invention, the optionally substituted hydrocarbyl group Y is one or more of carbonyl, carboxyl, nitro, hydroxy, halo, alkoxy, tertiary amino (no NH bond), oxy, cyano, sulfonyl, sulfoxyl, and the like. These functional groups may be contained. Most of the atoms in the substituted hydrocarbyl group, other than hydrogen, are generally carbon, and heteroatoms (eg, oxygen, nitrogen and sulfur) account for a small portion of all non-hydrogen atoms present, up to about 33%. It's just a general representation.

A functional group such as hydroxy, halo, alkoxy, nitro and cyano in the substituted hydrocarbyl group Y replaces one of the hydrogen atoms of the hydrocarbyl, but carbonyl, carboxyl, tertiary amino (—N—), oxy in the substituted hydrocarbyl group. Those skilled in the art will appreciate that functional groups such as sulfonyl and sulfoxyl replace the —CH— or CH ₂ — moiety of hydrocarbyl.

The hydrocarbyl group Y in formula (I) is more preferably unsubstituted or substituted with a group selected from hydroxy, halo or alkoxy groups, still more preferably C _1-4 alkoxy.

  Most preferably, the optionally substituted hydrocarbyl group Y in formula (I) is derived from a naturally occurring oil such as a stearyl group, 12-hydroxystearyl group, oleyl group, 12-hydroxyoleyl group or tall oil fatty acid. It is a group.

  The preparation of poly (hydroxycarboxylic acids) and derivatives thereof is known and is described in the art, for example in EP 0 164 817.

The poly (hydroxycarboxylic acid) of formula (I) can be prepared according to well-known methods, optionally in the presence of a catalyst (II)
HO-A-COOH (II)
(Wherein A is a divalent optionally substituted hydrocarbyl group)
May be produced by transesterification of one or more of the hydroxycarboxylic acids. Such methods are described, for example, in US Pat. No. 3,996,059, British Patent 1 373 660 and British Patent 1 342 746.

  The chain terminator in the transesterification may be a non-hydroxy carboxylic acid.

  The hydroxyl group in the hydroxy carboxylic acid and the carboxylic acid group in the hydroxy carboxylic acid or non-hydroxy carboxylic acid may be primary, secondary or tertiary in character.

  Transesterification of hydroxycarboxylic acids and non-hydroxycarboxylic acid chain terminators is accomplished by heating the starting material and azeotropically removing the water formed, optionally in a suitable hydrocarbon solvent such as toluene or xylene. Can be achieved. The reaction may be carried out at a temperature below −250 ° C., conveniently at the reflux temperature of the solvent.

  If the hydroxyl group in the hydroxycarboxylic acid is secondary or tertiary, the temperature used should not be so high as to cause dehydration of the acid molecule.

  The temperature at which a catalyst for transesterification, such as p-toluenesulfonic acid, zinc acetate, zirconium naphthenate or tetrabutyl titanate, increases the rate of reaction at a given temperature or is required for a given rate of reaction May be included for either purpose of lowering.

  In the compounds of formulas (I) and (II), A is preferably an optionally substituted aromatic, aliphatic or alicyclic linear or branched divalent hydrocarbyl group. Preferably A is an arylene, alkylene or alkenylene group, in particular in the range of 4-25 carbon atoms, more preferably in the range of 6-25 carbon atoms, more preferably in the range of 8-24 carbon atoms, More preferred are arylene, alkylene or alkenylene groups containing in the range of 10 to 22 carbon atoms, most preferably in the range of 12 to 20 carbon atoms.

  Preferably, in said compounds of formulas (I) and (II), at least 4 carbon atoms, more preferably at least 6 carbon atoms, directly linked between the carbonyl group and the oxygen atom derived from the hydroxyl group Still more preferably, there are in the range of 8 to 14 carbon atoms.

In the compounds of formulas (I) and (II), the optional substituents in group A are preferably selected from hydroxy, halo or alkoxy groups, more preferably _C1-4 alkoxy groups.

  The hydroxyl group in the hydroxycarboxylic acid of formula (II) is preferably a secondary hydroxyl group.

  Examples of suitable hydroxycarboxylic acids are 9-hydroxystearic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, 12-hydroxy-9-oleic acid (ricinoleic acid), 6-hydroxycaproic acid, preferably 12- Hydroxy stearic acid. Commercially available 12-hydroxystearic acid (hydrogenated castor oil fatty acid) usually contains 15% wt or less of stearic acid and other non-hydroxy carboxylic acids as impurities and is further added to produce a polymer having a molecular weight of about 1000-2000. Can be conveniently used without the admixture.

  If the non-hydroxy carboxylic acid is introduced separately into the reaction, the proportion required to produce a polymer or oligomer of a given molecular weight is determined either by simple experimentation or by calculation by one skilled in the art. be able to.

  The group (—O—A—CO—) in the compounds of the formulas (I) and (II) is preferably a 12-oxystearyl group, a 12-oxyoleyl group or a 6-oxycaproyl group.

  Preferred poly (hydroxycarboxylic acids) of formula (I) for reaction with amines include poly (hydroxystearic acid) and poly (hydroxyoleic acid).

  Suitable compounds having a terminal carboxylic acid group of the poly (hydroxycarboxylic acid) of formula (I) and a group that reacts with a terminal acid group selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate include: Suitable precursors of terminal acid groups include alpha-amino- or alpha-hydroxy-alkanecarboxylic acids such as glycine and glycolic acid, and amino- and hydroxy-organic sulfonic acids or phosphonic acids such as aminoethanesulfonic acid. Suitable bifunctional linking compounds that can form a linking group between the polyester and the terminal acid group are polyamines, polyols, hydroxylamines and Z as described above. It is a group.

Suitable compounds having a terminal carboxylic acid group of the poly (hydroxycarboxylic acid) of formula (I) and a group that reacts with a terminal acid group selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate;
The reaction of a terminal acid group precursor; or a bifunctional linking compound that is subsequently reacted with a terminal acid group precursor and a poly (hydroxycarboxylic acid) of formula (I) is well known in the art, For example, it is described in European Patent 0 164 817.

  A poly (hydroxycarboxylic acid) derivative having a terminal acid group, which is preferable in the present invention, is 60 mg. As measured by ASTM D 4739. Less than KOH / g, more preferably 50 mg. Less than KOH / g, still more preferably 40 mg. Less than KOH / g, most preferably 30 mg. Each has a TBN (total base number) value of less than KOH / g. Conveniently, the poly (hydroxycarboxylic acid) derivative having a terminal acid group is 5 mg. As measured by ASTM D 4739. Less than KOH / g, more conveniently 2 mg. Each may have a TBN value of KOH / g or less.

  In the present invention, a poly (hydroxycarboxylic acid) derivative having a terminal acid group is preferably 70 mg. Less than KOH / g, more preferably 60 mg. Less than KOH / g, still more preferably 50 mg. Less than KOH / g, most preferably 40 mg. Each has an acid value of less than KOH / g.

  In the liquid fuel composition of the present invention, when the base fuel used is gasoline, the gasoline can be any gasoline (petrol) type known in the art and suitable for use in spark ignition internal combustion engines. It may be. The gasoline used as the base fuel in the liquid fuel composition of the present invention may conveniently be referred to as “base gasoline”.

  Gasoline typically contains a mixture of hydrocarbons boiling in the range of 25-230 ° C. (EN-ISO 3405), with optimal ranges and distillation curves generally varying with the climate and season of the year. The hydrocarbons in the gasoline may be derived by any method known in the art, conveniently the hydrocarbon is straight run gasoline, a synthetically produced aromatic hydrocarbon mixture, thermal or catalytic cracking. It can be derived in any known manner from hydrocarbons, hydrocracked petroleum fractions, catalytically reformed hydrocarbons or mixtures thereof.

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

  Conveniently, the research octane number (RON) of the gasoline may be at least 80, for example in the range 80-110, preferably the gasoline RON is in the range of at least 90, for example 90-110, more preferably the gasoline. RON is at least 91, for example in the range 91-105, even more preferably gasoline RON is in the range of at least 92, for example 92-103, and even more preferably gasoline RON is at least 93, for example 93- 102, most preferably the gasoline RON is at least 94, for example in the range 94-100 (EN 25164); the gasoline motor octane number (MON) is advantageously at least 70, for example 70-110. May be in range, preferably gasoline M N is in the range of at least 75, such as 75-105, more preferably the gasoline MON is in the range of at least 80, such as 80-100, and most preferably the gasoline MON is at least 82, such as 82-95. It is in range (EN 25163).

  In general, gasoline includes a component selected from one or more of the following groups: saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and oxygenated hydrocarbons. Conveniently, the gasoline may contain a mixture of saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and optionally oxygenated hydrocarbons.

  Generally, the olefinic hydrocarbon content of gasoline is in the range of 0 to 40 volume percent based on gasoline (ASTM D1319); preferably, the olefinic hydrocarbon content of gasoline is based on gasoline. More preferably, the olefinic hydrocarbon content of the gasoline is in the range of 0-20 volume percent based on gasoline.

  In general, the aromatic hydrocarbon content of gasoline is in the range of 0 to 70 volume percent based on gasoline (ASTM D1319), for example, the aromatic hydrocarbon content of gasoline is 10 based on gasoline. Preferably, the gasoline aromatic hydrocarbon content is in the range of 0-50 volume percent based on gasoline, for example, the gasoline aromatic hydrocarbon content is As a standard, it is in the range of 10 to 50 volume percent.

  The benzene content of gasoline is 10 volume percent or less, more preferably 5 volume percent or less, especially 1 volume percent or less, based on gasoline.

  The gasoline preferably has a low or ultra-low sulfur content, such as 1000 ppmw (parts per million by weight) or less, preferably 500 ppmw or less, more preferably 100 or less, even more preferably 50 or less, most preferably still 10 ppmw or less. Have

  The gasoline also preferably has a low total lead content, such as 0.005 g / l or less, and most preferably contains no lead, ie no lead compound is added to it (ie it is unleaded).

  When gasoline contains oxygenated hydrocarbons, at least some of the oxygen free hydrocarbons are replaced with oxygenated hydrocarbons. The oxygen content of gasoline may be 35 weight percent or less (EN 1601) (eg, ethanol itself) based on gasoline. For example, the oxygen content of gasoline may be 25 weight percent or less, preferably 10 weight percent or less. Conveniently, the oxygenate concentration is a minimum concentration selected from any of 0, 0.2, 0.4, 0.6, 0.8, 1.0, and 1.2 weight percent, and 5 , 4.5, 4.0, 3.5, 3.0, and 2.7 weight percent.

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

  When oxygenated hydrocarbons are present in the gasoline, the amount of oxygenated hydrocarbons in the gasoline may vary over a wide range. For example, gasolines containing a major proportion of oxygenated hydrocarbons such as ethanol itself and E85, and minor proportions of oxygenated hydrocarbons such as gasoline containing E10 and E5 are currently commercially available in countries such as Brazil and the United States. It is available. Therefore, gasoline may contain up to 100 volume percent oxygenated hydrocarbons. Preferably, the amount of oxygenated hydrocarbon present in the gasoline is selected from one of the following amounts: 85 volume percent or less; 65 volume percent or less; 30 depending on the desired final formulation of the gasoline; 30 20 volume percent or less; 15 volume percent or less; and 10 volume percent or less. Conveniently, the gasoline may contain at least 0.5, 1.0 or 2.0 volume percent oxygenated hydrocarbons.

  Examples of suitable gasolines include 0-20 volume percent olefinic hydrocarbon content (ASTM D1319), 0-5 weight percent oxygen content (EN 1601), 0-50 volume percent aromatic hydrocarbon content. Gasoline having a rate (ASTM D1319) and a benzene content of 1 volume percent or less.

  While not critical to the present invention, the base gasoline or gasoline composition of the present invention may conveniently further contain one or more fuel additives. The concentration and nature of the fuel additive that may be included in the base gasoline or gasoline composition of the present invention is not critical. Non-limiting examples of suitable types of fuel additives that can be included in the base gasoline or gasoline composition of the present invention include antioxidants, corrosion inhibitors, cleaning agents, dehaze agents, antiknocks Additives, metal deactivators, valve seat retraction inhibitor compounds, dyes, friction modifiers, carrier fluids, diluents and markers. Examples of suitable such additives are generally described in US Pat. No. 5,855,629.

  Conveniently, the fuel additive can be blended with one or more diluents or carrier fluids to form the additive concentrate, which is then the base gasoline or gasoline of the present invention. Can be mixed with the composition.

  The (active ingredient) concentration of any additive present in the base gasoline or gasoline composition of the present invention is preferably no more than 1 weight percent, more preferably in the range of 5-1000 ppmw, advantageously such as 95-150 ppmw. 75 to 300 ppmw.

  In the liquid fuel composition of the present invention, when the base fuel used is a diesel fuel, the diesel fuel used as the base fuel in the present invention includes those used in automobile compression ignition engines, and for example, marine, railway and stationary engines. Includes diesel fuel for use in other types of engines. The diesel fuel used as a base fuel in the liquid fuel composition of the present invention may also conveniently be referred to as a “diesel base fuel”.

  The diesel base fuel may itself contain a mixture of two or more different diesel fuel components and / or may be supplemented as described below.

Such diesel fuels contain one or more base fuels that may typically contain liquid hydrocarbon middle distillate gas oils, such as petroleum-derived gas oils. Such fuels generally have boiling points within the normal diesel range of 150-400 ° C., depending on brand and application. The They generally at 15 ℃, 750~1000kg / ^{m 3,} preferably a density (e.g. ASTM D4502 or IP 365) of 780~860kg / ^{m 3,} and from 35 to 120, more preferably cetane 40-85 Value (ASTM D613). They generally have an initial boiling point in the range of 150-230 ° C and a final boiling point in the range of 290-400 ° C. Their kinematic viscosity at 40 ° C. (ASTM D445) may suitably be 1.2-4.5 mm ² / sec.

Examples of petroleum-derived gas oils have a density of 800-820 kg / m ³ at 15 ° C. (SS-EN ISO 3675, SS-EN ISO 12185), T95 below 320 ° C., as defined in the Swedish national standard EC1. Swedish Class 1 base fuel with (SS-EN ISO 3405) and kinematic viscosity at 40 ° C. (SS-EN ISO 3104) of 1.4-4.0 mm ² / sec.

  Optionally, non-mineral oil based fuels such as biofuels or Fischer-Tropsch derived fuels may also form or be present in the diesel fuel. Such Fischer-Tropsch fuels may be derived, for example, from natural gas, natural gas liquids, petroleum or shale oil, petroleum or shale oil treatment residues, coal or biomass.

  The amount of Fischer-Tropsch derived fuel used for diesel fuel may be 0% to 100% v, preferably 5% to 100% v, more preferably 5% to 75% v of the total diesel fuel. It may be desirable for such diesel fuel to contain a Fischer-Tropsch derived fuel of 10% v or more, more preferably 20% v or more, and even more preferably 30% v or more. It is particularly preferred that such diesel fuel contains 30 to 75% v, in particular 30 or 70% v Fischer-Tropsch derived fuel. The remainder of the diesel fuel is composed of one or more other diesel fuel components.

  Such Fischer-Tropsch derived fuel component is any fraction of the middle distillate fuel range that can be isolated from the (optionally hydrocracked) Fischer-Tropsch synthesis product. Typical fractions boil in the naphtha, kerosene or gas oil range. Preferably, Fischer-Tropsch products boiling in the kerosene or gas oil range are used. This is because these products are easier to handle in a home environment, for example. Such products suitably comprise more than 90% by weight fraction boiling to 160-400 ° C, preferably up to about 370 ° C. Examples of Fischer-Tropsch derived kerosene and gas oil are described in European Patent Application Publication No. A-0583836, International Publication No. A-97 / 14768, International Publication No. A-97 / 14769, International Publication No. A. -00/11116 pamphlet, WO-A-00 / 11117 pamphlet, WO-A-01 / 83406 pamphlet, WO-A-01 / 83648 pamphlet, WO-A-01 / 83647 pamphlet. , International Publication No. A-01 / 833641, Pamphlet of International Publication No. A00 / 20535, Pamphlet of International Publication No. A-00 / 20534, European Patent Application Publication No. A-1101813, US Pat. No. 5,766,274. Specification, US Pat. No. 5,378,348 Specification, are described in U.S. Pat. No. 5888376 and U.S. Patent No. 6,204,426.

  The Fischer-Tropsch product preferably contains more than 80% by weight, more preferably more than 95% by weight of iso and normal paraffins and less than 1% by weight of aromatic compounds, the rest being naphthenic compounds. The sulfur and nitrogen content is very low, usually below the detection limit of such compounds. For this reason, the sulfur content of diesel fuel compositions containing Fischer-Tropsch products can be very low.

  The diesel fuel composition is preferably 5000 ppmw or less, more preferably 500 ppmw or less, or 350 ppmw or less, or 150 ppmw or less, or 100 ppmw or less, or 70 ppmw or less, or 50 ppmw or less, or 30 ppmw or less, or 20 ppmw or less, or most preferably Contains 15 ppmw or less of sulfur.

  The diesel base fuel may itself be added with additives (containing additives) or unadded (without additives). For example, if the additive is added at a refinery, it may be an antistatic agent, a pipeline drag reducer, a flow improver (eg, ethylene / vinyl acetate copolymer or acrylate / maleic anhydride copolymer), lubricating additive, oxidation Contains one or more small amounts of additives selected, for example, from inhibitors and wax settling inhibitors.

  Detergent-containing diesel fuel additives are known and are commercially available. Such additives may be added to diesel fuel at a level that is intended to reduce, eliminate, or slow down the accumulation of engine deposits.

  Examples of detergents suitable for use in diesel fuel additives for current purposes include polyolefin substituted succinimides or succinimides of polyamines such as polyisobutylene succinimide or polyisobutylene amine succinimide, aliphatic amines, Mannich bases or amines and polyolefins (For example, polyisobutylene) maleic anhydride. Succinimide dispersant additives include, for example, GB-A-960493, European Patent Application Publication No. A-0147240, European Patent Application Publication No. A-0482253, European Patent Application Publication No. A-0613938, This is described in EP-A-0557516 and WO-A-98 / 42808. Polyolefin-substituted succinimides such as polyisobutylene succinimide are particularly preferred.

  The diesel fuel additive mixture may contain other components in addition to the detergent. Examples include lubricity enhancers; defoaming agents such as alkoxylated phenol formaldehyde polymers; antifoaming agents such as polyether modified polysiloxanes; ignition improvers (cetane improvers) such as 2-ethylhexyl nitrate (EHN), Cyclohexyl nitrate, di-tert-butyl peroxide and U.S. Pat. No. 4,208,190, disclosed in column 2, lines 27-3, line 21); rust inhibitors (e.g. tetrapropenyl succinate) Propane-1,2-diol half ester of acid, or polyhydric alcohol ester of succinic acid derivative, unsubstituted or substituted aliphatic hydrocarbon containing 20-500 carbon atoms in at least one of its alpha-carbon atoms Group-containing succinic acid derivatives, eg polyisobutylene substituted succinic acid pentaerythr Toll diester); corrosion inhibitor; flavoring agent; antiwear agent; antioxidant (eg phenolic compound such as 2,6-di-tert-butylphenol, or N, N′-di-tert-butyl-p-phenylene) Phenylenediamines such as diamines); metal deactivators; auxiliary agents; static dissipators; low temperature fluidity improvers;

The diesel fuel additive mixture may contain a lubricity enhancer, especially when the diesel fuel composition has a low sulfur content (eg, 500 ppmw or less). In diesel fuel compositions with additives, the lubricity enhancer is conveniently present at a concentration of less than 1000 ppmw, preferably 50-1000 ppmw, more preferably 70-1000 ppmw. Suitable commercially available lubricity enhancers include ester- and acid-based additives. Other lubricity enhancers are described in the patent literature, for example in connection with their use, particularly with low sulfur content diesel fuels:
-Danping Wei and H.C. A. An article by Spikes, “The Lubricity of Diesel Feuls”, Wear, III (1986) pp. 217-235;
-WO-A-95 / 33805-Low temperature fluidity improver to enhance the lubricity of low sulfur fuels;
-WO-A-94 / 17160-Carboxylic acid has 2 to 50 carbon atoms and alcohol is one or more carbons as a fuel additive for wear reduction in diesel engine injection systems Certain esters of carboxylic acids with atoms and alcohols, in particular glycerol monooleate and di-isodecyl adipate;
-U.S. Patent No. 5,490,864-Certain dithiophosphoric acid diesters-dialcohols as anti-wear lubricant additives for low sulfur diesel fuels; and-International Publication No. A-98 / 01516 In particular, certain alkyl aromatic compounds in which at least one carboxyl group is bonded to their aromatic nucleus are described to provide anti-wear lubricity effects for low sulfur diesel fuels.

  It may also be preferred for diesel fuel compositions to contain an antifoam agent, more preferably in combination with a rust inhibitor and / or corrosion inhibitor and / or lubricity enhancing additive.

  Unless otherwise stated, the (active ingredient) concentration of each such additive component in the diesel fuel composition to which the additive has been added is preferably 10000 ppmw or less, more preferably 0.1 to 1000 ppmw, advantageously 0. In the range of 0.1 to 300 ppmw, such as 1 to 150 ppmw.

  The (active ingredient) concentration of any defoamer in the diesel fuel composition is preferably in the range of 0.1-20 ppmw, more preferably 1-15 ppmw, even more preferably 1-10 ppmw, advantageously 1-5 ppmw. It is in. The (active ingredient) concentration of any ignition improver present is preferably 2600 ppmw or less, more preferably 2000 ppmw or less, conveniently 300-1500 ppmw. The (active ingredient) concentration of any detergent in the diesel fuel composition is preferably in the range of 5 to 1500 ppmw, more preferably 10 to 750 ppmw, and most preferably 20 to 500 ppmw.

In the case of a diesel fuel composition, for example, the fuel additive mixture generally contains a cleaning agent and a diesel fuel compatible diluent, optionally in conjunction with the other components described above. , Mineral oils, solvents such as those sold by Shell under the trademark “SHELLSOL”, polar solvents such as esters, and in particular alcohols such as hexanol, 2-ethylhexanol, decanol, isotridecanol and the trademark “LINEVOL”, It may be an alcohol mixture such as those sold by Shell company, especially LINEVOL 79 alcohol, which is a mixture of C _7-9 primary alcohols, or a commercially available C _12-14 alcohol mixture.

  The total content of additives in the diesel fuel composition may suitably be from 0 to 10,000 ppmw, preferably less than 5000 ppmw.

  In the above, the component amounts (concentration,% vol, ppmw,% wt) are those of the active ingredient, i.e. excluding the volatile solvent / diluent material.

  The liquid fuel composition of the present invention is produced by mixing one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups with a base fuel suitable for use in an internal combustion engine. If the base fuel to which one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups are mixed is gasoline, the resulting liquid fuel composition is a gasoline composition; likewise, it has terminal acid groups When the base fuel into which one or more poly (hydroxycarboxylic acid) derivatives are mixed is a diesel fuel, the resulting liquid fuel composition is a diesel fuel composition.

Preferably, the amount of one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups present in the liquid fuel composition of the present invention is at least 1 ppmw (by weight) based on the total weight of the liquid fuel composition. Part per million). More preferably, the amount of one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups present in the liquid fuel composition of the present invention is one or more of the following parameters (i) to (xx): Matches:
(I) at least 10 ppmw
(Ii) at least 20 ppmw
(Iii) at least 30 ppmw
(Iv) at least 40 ppmw
(V) at least 50 ppmw
(Vi) at least 60 ppmw
(Vii) at least 70 ppmw
(Viii) at least 80 ppmw
(Ix) at least 90 ppmw
(X) at least 100 ppmw
(Xi) 20% wt. The following (xii) 18% wt. (Xiii) 16% wt. (Xiv) 14% wt. (Xv) 12% wt. (Xvi) 10% wt. (Xvii) 8% wt. (Xviii) 6% wt. (Xix) 4% wt. (Xx) 2% wt. Less than

  Conveniently, the amount of one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups present in the liquid fuel composition of the present invention is also at least 200 ppmw, at least 300 ppmw, at least 400 ppmw, at least 500 ppmw, or even It may be at least 1000 ppmw.

  Surprisingly, the use of one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups in the liquid fuel composition is particularly advantageous when the liquid fuel composition is gasoline relative to the liquid base fuel. It has been found that significant benefits can be provided in terms of improved lubricity of the fuel composition.

  As used herein, the term “improved / improved lubricity” means that wear scars generated using a high frequency reciprocating rig (HFRR) are reduced.

  The use of one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups in a liquid fuel composition also makes the liquid fuel composition of the present invention in comparison to an internal combustion engine fueled with a liquid base fuel. It has further been found that benefits can be provided from the standpoint of engine cleanliness of an internal combustion engine being fueled, particularly from the standpoint of improved inlet valve deposition cleanliness and / or injector nozzle cleanliness retention.

  The term “improved / enhanced inlet valve deposition cleanliness retention performance” refers to one or more poly (hydroxycarboxylic acid) derivatives in which the weight of deposit formed on the engine inlet valve has terminal acid groups. It means that it is reduced compared to the base fuel that does not contain.

  The term “improved / enhanced injector nozzle cleanliness retention performance” means that the amount of deposit formed on the injector nozzle of the engine is reduced as measured by the loss of engine torque. To do.

  The use of one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups in a liquid fuel composition also makes the liquid fuel composition of the present invention in comparison to an internal combustion engine fueled with a liquid base fuel. It has further been found that benefits can be provided in terms of improved fuel savings for internal combustion engines being fueled.

  The present invention therefore also uses in an internal combustion engine comprising mixing one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups with a major amount of liquid-based fuel suitable for use in the internal combustion engine. And a method of improving the lubricity of a liquid-based fuel suitable for use with one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups with a major amount of liquid-based fuel suitable for use in an internal combustion engine. Suitable methods for improving inlet valve deposition cleanliness performance of liquid-based fuels suitable for use in internal combustion engines and one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups are suitable for use in internal combustion engines A method for improving the nozzle cleanliness retention performance of a liquid-based fuel injector suitable for use in an internal combustion engine, including mixing with a major amount of liquid-based fuel, and one or more poly (hydrides) having terminal acid groups Comprising the Kishikarubon acid) derivative is mixed with a major amount of a suitable liquid base fuel for use in internal combustion engines, to provide a method for improving fuel economy performance of the preferred liquid base fuel for use in internal combustion engines.

  Further, the use of one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups in the liquid fuel composition also provides for the liquid fuel composition of the present invention compared to an internal combustion engine that is being fueled with a liquid based fuel. It has been found that it can provide benefits in terms of improving the lubricating oil performance of an internal combustion engine that is being fueled.

In particular, improved lubricating oil performance of an internal combustion engine fueled with a liquid fuel composition according to the present invention includes rocker arm covers, cam baffles, timing chain covers, oil pans, oil pan baffles, sludge on bubble decks, and pistons. It can be observed by a decrease in the level of sludge and varnish on certain engine parts, such as varnish on the skirt and cam baffle.

  In particular, the use of one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups in gasoline compositions fuels the gasoline composition of the present invention compared to internal combustion engines that are being fueled with gasoline-based fuels. Benefits can be provided in terms of inhibiting the formation of certain sludge and varnish deposits, as measured by ASTM D 6593-07, of the internal combustion engine being supplied.

  Therefore, the present invention also provides a method for improving the performance of a lubricating oil in an internal combustion engine, comprising supplying the liquid fuel composition according to the present invention to an internal combustion engine containing the engine lubricating oil. .

  The invention further provides a method of operating an internal combustion engine comprising introducing a liquid fuel composition according to the invention into the combustion chamber of the engine.

  The poly (hydroxycarboxylic acid) derivatives having terminal acid groups as described above may also be advantageously used in lubricating compositions, particularly in automotive engine lubricating oil compositions. WO 2007/128740, which is incorporated herein by reference, discloses suitable lubricating base oils and additives that can be mixed with poly (hydroxycarboxylic acid) derivatives having terminal acid groups as described above. .

Therefore, the present invention
-Base oil;
-Further providing a lubricating composition comprising a poly (hydroxycarboxylic acid) derivative having a terminal acid group as described above.

  Generally, the poly (hydroxycarboxylic acid) derivative having a terminal acid group is in an amount in the range of 0.1 to 10.0 wt%, more preferably 0.1, based on the total weight of the lubricating composition. It is present in the lubricating composition of the present invention in an amount ranging from ˜5.0% by weight. According to an especially preferred embodiment, the composition is a poly (hydroxycarboxylic acid) having terminal acid groups of less than 5.0% by weight, preferably less than 2.0% by weight, based on the total weight of the lubricating composition. Including derivatives.

  Generally, the lubricating composition has a relatively low phosphorus content (according to ASTM D 5185), such as less than 0.12% by weight. Preferably the composition has a phosphorus content of less than 0.08% by weight. Preferably the composition has a phosphorus content greater than 0.06% by weight.

  The composition also preferably has a sulfur content of less than 0.6% by weight (according to ASTM D 5185).

  Furthermore, the composition preferably has a chlorine content (according to ASTM D 808) of less than 200 ppm.

  According to an especially preferred embodiment, the composition has an ash content (according to ASTM D 874) of less than 2.0% by weight.

  According to an especially preferred embodiment of the present invention, the composition comprises a zinc dialkyldithiophosphate (ZDDP) compound. Generally, when present, the ZDDP compound is present in an amount of 0.01 to 1.5 wt%, preferably 0.4 to 1.0 wt%. ZDDP compounds may be made from primary, secondary, tertiary alcohols or mixtures thereof, preferably containing less than 12 carbon atoms. Preferably, the ZDDP compound is made from a secondary alcohol containing 3-8 carbon atoms.

  There are no particular restrictions on the base oil used in the lubricating composition, and various conventional mineral oils, synthetic oils and naturally derived esters such as vegetable oils can be advantageously used.

  The base oil used may conveniently comprise a mixture of one or more mineral oils and / or one or more synthetic oils, and thus the term “base oil” is a mixture containing two or more base oils. Can mean. Mineral oils include liquid petroleum that can be further refined by hydrorefining and / or dewaxing, as well as paraffinic, naphthenic, or mixed paraffinic / naphthenic type solvent-treated or acid-treated mineral lubricating oils.

  Suitable base oils for use in lubricating oil compositions are Group I-III mineral base oils, Group IV poly-alpha olefins (PAO), Group II-III Fischer-Tropsch derived base oils and mixtures thereof. .

  “Group I”, “Group II”, “Group III” and “Group IV” base oils are lubricant base oils in accordance with the American Petroleum Institute (API) definition for categories I-IV. Means. These API categories are defined in API Publication 1509, 16th edition, Appendix E, April 2007.

  Fischer-Tropsch derived base oils are known in the art. The term “derived from Fischer-Tropsch” means that the base oil is or is derived from a synthetic product of the Fischer-Tropsch process. Fischer-Tropsch derived base oils may also be referred to as GTL (Gas-To-Liquids) base oils. Suitable Fischer-Tropsch derived base oils which can advantageously be used as base oils in lubricating compositions are, for example, 0 776 959, EP 0 668 342, WO 97/21788, International Publication No. 00/15736, International Publication No. 00/14188, International Publication No. 00/14187, International Publication No. 00/14183, International Publication No. 00/14179, International Publication No. 00/08115 No. pamphlet, WO 99/41332 pamphlet, EP 1 029 029 specification, WO 01/18156 pamphlet and WO 01/57166 pamphlet.

  Synthetic oils include hydrocarbon oils such as olefin oligomers (polyalphaolefin base oils; including PAO), dibasic acid esters, polyol esters, polyalkylene glycols (PAG), alkylnaphthalenes and dewaxed waxy isomers. Is included. A synthetic hydrocarbon base oil sold by Shell Group under the designation “Shell XHVI” ™ may be used conveniently.

Poly-alpha olefin base oils (PAO) and their manufacture are well known in the art. Preferred poly can be used in the lubricating compositions - alpha olefin base oil, linear _C 2 _{-C 32,} preferably may be derived from _C 6 _{-C 16} alpha-olefins. Particularly preferred raw materials for the poly-alphaolefin are 1-octene, 1-decene, 1-dodecene and 1-tetradecene.

  The total amount of base oil incorporated into the lubricating composition is preferably in the range of 60 to 99% by weight, more preferably in the range of 65 to 98% by weight, based on the total weight of the lubricating composition. Preferably it is present in an amount ranging from 70 to 95% by weight.

Preferably, the finished lubricating composition, in the range of 2~80mm ² / s at 100 ° C., more preferably in the range of 3~70mm ² / sec, and most preferably a kinematic viscosity in the range of 4~50mm ² / sec Have.

  Lubricating compositions include antiwear additives, antioxidants, dispersants, detergents, friction modifiers, viscosity index improvers, pour point depressants, corrosion inhibitors, antifoaming agents and sealing fixatives or sealing compatibilizers. Additional additives such as may also be included.

  As those skilled in the art are familiar with these and other additives, these are not further discussed herein in detail. Specific examples of such additives are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, volume 14, pages 477-526.

  Preferably, the detergent, if present, is appropriately selected from phenoxide type and sulfonate type detergents.

  The lubricating composition comprises a poly (hydroxycarboxylic acid) derivative having a terminal acid group as described above, and optionally any further that is normally present in the lubricating composition, eg, as previously described herein. Additives can be conveniently prepared by mixing with minerals and / or synthetic base oils.

  The use of a poly (hydroxycarboxylic acid) derivative having a terminal acid group as described above in a lubricating composition can provide benefits from the viewpoint of improved lubricity of the lubricating composition.

  Furthermore, the use of the above-mentioned poly (hydroxycarboxylic acid) derivatives having terminal acid groups in lubricating compositions is said to inhibit the formation of certain sludge and varnish deposits as measured by ASTM D 6593-07. From the point of view, it can provide benefits.

  Furthermore, the use of the above-mentioned poly (hydroxycarboxylic acid) derivative having a terminal acid group in a lubricating composition provides benefits from the viewpoint of improving the fuel economy of an internal combustion engine lubricated with the lubricating composition. can do.

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

  In the following examples, a commercially available superdispersant, CH-2C, is available from Shanghai Sanzheng Polymer Material Co Ltd (China).

The CH-2C superdispersant has an average molecular weight of 1368, a measured sulfur content of 0.61 ppmw, 0.05% wt. Measured nitrogen content, and

Figure 1: It had a general chemical structure of the type shown in CH-2C.

Examples 1 to 21 and Comparative Examples A to D
The above CH-2C superdispersant was blended in various amounts into a base fuel selected from gasoline, diesel, GTL diesel and Swedish Class I diesel base fuels listed in Tables 1 and 2 below.

  In order to evaluate the lubricity of the liquid fuel composition described above, the following test procedure was used.

  The lubricity of the diesel fuel composition was measured using the HFRR test used, described in ISO 12156-1.

  The lubricity of the gasoline composition was measured by using a modified HFRR test. The modified HFRR test is based on ISO 12156-1, using a PCS equipment HFRR supplemented with a PCS Instruments Gasoline Conversion Kit and a fluid volume of 15.0 ml (± 0.2 ml), 25. A fluid temperature of 0 ° C. (± 1 ° C.) is used, and here a PTFE cover is used to cover the test sample to minimize evaporation.

The results of the lubricity test are shown in Table 3 below.

  As can be seen from the results in Table 3, a reduction in wear scars for fuel compositions (both gasoline and diesel fuel compositions) containing CH-2C superdispersant was observed in the HFRR test compared to the base fuel. It represents an improvement in the lubricity of a fuel containing a superdispersant compared to a base fuel.

European Patent Application Publication No. 0164817 A2 European Patent Application Publication No. 0233684 A1 UK Patent Application Publication No. 2197312A European Patent Application Publication No. 0802255 A2 International Publication No. 00/34418 A1 International Publication No. A-97 / 14768 International Publication No. A-97 / 14769 International Publication No. A-00 / 11116 International Publication No. A-00 / 11117 International Publication No. A-01 / 83406, International Publication No. A-01 / 83648 International Publication No. A-01 / 83647 International Publication No. A-01 / 83641 International Publication No. A-00 / 20535 International Publication No. A-00 / 20534, International Publication No. A-95 / 33805 International Publication No. A-94 / 17160 International Publication No. A-98 / 01516 International Publication No. 97/21788 International Publication No. 01/57166 International Publication No. 01/18156 International Publication No. 00/15736 International Publication No. 00/14188 International Publication No. 00/14187 International Publication No. 00/14183 International Publication No. 00/14179 International Publication No. 00/08115 International Publication No. 99/41332 European Patent No. 0 164 817 European Patent Application Publication No. A-0583836 European Patent Application Publication No. A-1101813 European Patent No. 0 776 959 European Patent No. 0 668 342 European Patent No. 1 029 029 US Pat. No. 3,996,059 US Pat. No. 5,766,274 US Pat. No. 5,378,348 US Pat. No. 5,888,376 US Pat. No. 6,204,426 US Pat. No. 5,490,864 British Patent No. 1 373 660 British Patent No. 1 342 746

Danping Wei and H.C. A. An article by Spikes, “The Lubricity of Diesel Feuls”, Wear, III (1986) pp. 217-235. Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, volume 14, pages 477-526

Claims (11)

-A base fuel suitable for use in an internal combustion engine;
-Formula (III):
_{[Y-CO [O-A} -CO] n -Z p] m -X (III)
Wherein Y is hydrogen or an optionally substituted hydrocarbyl group, A is a divalent optionally substituted hydrocarbyl group, n is 1 to 100, m is 1 or 2, Z is an optionally substituted divalent bridging group, p is 0 or 1, and X is a terminal acid group or terminal acid selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate It is a group that has a group)
One or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups having:
A liquid fuel composition comprising:   The amount of the one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups present in the liquid fuel composition of the present invention is at least 1 ppmw, based on the total amount of the liquid fuel composition; The liquid fuel composition according to claim 1.   The amount of the one or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups present in the liquid fuel composition of the present invention is 10 ppmw to 20% wt, based on the total amount of the liquid fuel composition. The liquid fuel composition according to claim 2, which is in the range of X is the formula -Z ¹ -X ¹ where Z ¹ is a bifunctional linking compound and X ¹ is a terminal acid group selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate The liquid fuel composition according to any one of claims 1 to 3, which is a group of The liquid fuel composition according to claim 4, wherein Z ¹ is a polyamine, polyol, hydroxylamine, or a bifunctional linking compound selected from the Z groups defined in claim 1.   The liquid fuel composition according to any one of claims 1 to 5, wherein the terminal acid group is in the form of a free acid.   The liquid fuel composition according to any one of claims 1 to 5, wherein the terminal acid group is in the form of a salt of the acid.   The liquid fuel composition according to claim 1, wherein the base fuel is gasoline.   The liquid fuel composition according to any one of claims 1 to 7, wherein the base fuel is a diesel fuel.   A method for operating an internal combustion engine, comprising introducing the liquid fuel composition according to any one of claims 1 to 9 into a combustion chamber of the engine. -Base oil;
-Formula (III):
_{[Y-CO [O-A} -CO] n -Z p] m -X (III)
Wherein Y is hydrogen or an optionally substituted hydrocarbyl group, A is a divalent optionally substituted hydrocarbyl group, n is 1 to 100, m is 1 or 2, Z is an optionally substituted divalent bridging group, p is 0 or 1, and X is a terminal acid group or terminal acid selected from carboxylic acid, carboxymethyl, sulfate, sulfonate, phosphate and phosphonate It is a group that has a group)
One or more poly (hydroxycarboxylic acid) derivatives having terminal acid groups having:
A lubricating composition comprising: