Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
  • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1608—Well defined compounds, e.g. hexane, benzene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy

Definitions

• the present invention relates to fuel additive compositions and fuel compositions as well as a method for fueling an internal combustion engine, providing reduced friction inside the engine and so improved fuel economy while also providing improved low temperature stability characteristics and handling properties of the fuel additive compositions.
• Fuel additives comprised of fatty acids and their derivatives are generally known to effectively improve fuel economy by reducing internal friction losses in an engine.
• concentrated additive packages containing such materials tend to have poor low temperature storage stability. This poor low temperature storage stability is seen in the formation of solids, sediments and/or thick gels in the additive packages containing these materials. This low temperature storage stability results in poor handling characteristics of packages containing these additives, especially in northern and/or cooler climates where the packages may be regularly exposed to cooler temperatures.
• U.S. Pat. No. 4,326,972, Chamberlin, Apr. 27, 1982 discloses lubricant compositions for improving fuel economy of internal combustion engines.
• the composition includes a specific sulfurized composition (based on an ester of a carboxylic acid) and a basic alkali metal sulfonate. Additional ingredients may include at least one oil and/or fuel-dispersible detergent or dispersant, a viscosity improving agent, and a specific salt of a phosphorus acid.
• the present invention solves these problems by providing an alternative type of friction modifier using derivatives of certain carboxylic acids.
• These alternative friction modifiers provide the same or better fuel economy improving performance while also exhibiting improved low temperature stability of the additive compositions in which they are used, eliminating the handling the problems seen with other fatty acid and fatty acid-derived friction modifiers.
• the present invention provides an additive composition for use in an internal combustion engine, comprising: (a) a friction modifier represented by Formula I; and further comprising (b) and optional solvent; and (c) one or more optional additional performance additives;
• Y and Y′ are independently —O—, >NH, >NR 3 , or an imide group formed by taking together both Y and Y′ groups and forming a R 1 —N ⁇ group between two >C ⁇ O groups;
• X is independently —Z—O—Z′—, >CH 2 , >CHR 4 , >CR 4 R 5 , >C(OH)(CO 2 R 2 ), >C(CO 2 R 2 ) 2 , >CHOR 6 , or >CHCO 2 R 2 ;
• Z and Z′ are independently >CH 2 , >CHR 4 , >CR 4 R 5 , >C(OH)(CO 2 R 2 ), or >CHOR 6 ;
• m is 0 or 1;
• R 1
• component (a), the friction modifier is a condensation product of (a)(i), a material represented by formula II and (a)(ii), a mixture comprising a branched alcohol or branched amine having 1 to about 150 carbon atoms, or combinations thereof;
• each X is independently —Z—O—Z—, >CH 2 , >CR 1 R 2 , or >CHOR 2 ; and wherein each Z is independently >CH 2 , >CR 1 R 2 , >C(OH)(CO 2 R 2 ), or >CHOR 2 ;
• m is 0 or 1;
• the X is >CHOR 2 and n is 2.
• (X) n is —CH 2 —C(OH)(CO 2 R 2 )—CH 2 —.
• the m in formula II is 1.
• component (a)(i) is tartaric acid, citric acid, derivatives of either acid, or combinations thereof.
• component (a)(ii) comprises a mixture of one or more branched alcohols or amines.
• the mixture comprises one or more branched alcohols where the alcohols contain from 6 to 16 carbon atoms.
• the mixture comprises branched amines containing 6 to 16 carbon atoms.
• component (a)(ii) is made up of a mixture of one or more branched alcohols or amines where the overall mixture is at least 25 percent by weight branched, in that at least 25 percent by weight of the alcohols and/or amines making up the mixture have a branched structure.
• the invention also provides a fuel composition comprising the fuel additive composition described herein.
• the invention also provides a method of operating an internal combustion engine, comprising supplying to said engine a fuel composition comprising any of the compositions described herein.
• the present invention involves a fuel additive composition, a fuel composition and a method for fueling an internal combustion engine, where the fuel additive includes a friction modifier (which may also be referred to as an antiwear agent) derived from the reaction of certain carboxylic acids and a mixture comprising one or more branched alcohols and/or branched amines having 1 to about 150 carbon atoms.
• a friction modifier which may also be referred to as an antiwear agent
• the fuel additive composition of the invention shows improved low temperature stability characteristic, thereby reducing additive handling issues.
• the additive composition may also be used in fuel compositions to provide reduced friction inside the engine and so improved fuel economy.
• the additive composition of the present invention comprises the friction modifier described herein and, in some embodiments, may further comprise a solvent and/or one or more additional performance additives.
• the solvents suitable for use in the present invention include hydrocarbon solvents that provide for the additive composition's compatibility and/or homogeneity and to facilitate their handling and transfer and may include a fuel as described below.
• the solvent can be an aliphatic hydrocarbon, an aromatic hydrocarbon, an oxygen-containing composition, or a mixture thereof.
• the flash point of the solvent is generally about 25° C. or higher.
• the hydrocarbon solvent is an aromatic naphtha having a flash point above 62° C. or an aromatic naphtha having a flash point of 40° C. or a kerosene with a 16% aromatic content having a flash point above 62° C.
• Aliphatic hydrocarbons include various naphtha and kerosene boiling point fractions that have a majority of aliphatic components.
• Aromatic hydrocarbons include benzene, toluene, xylenes and various naphtha and kerosene boiling point fractions that have a majority of aromatic components.
• Alcohols are usually aliphatic alcohols having about 2 to 10 carbon atoms and include ethanol, 1-propanol, isopropyl alcohol, 1-butanol, isobutyl alcohol, amyl alcohol, and 2-methyl-1-butanol.
• the oxygen containing composition can include an alcohol, a ketone, an ester of a carboxylic acid, a glycol and/or a polyglycol, or a mixture thereof.
• the solvent in an embodiment of the invention will be substantially free of to free of sulphur having a sulphur content in several instances that is below 50 ppm, 25 ppm, below 18 ppm, below 10 ppm, below 8 ppm, below 4 ppm, or below 2 ppm.
• the solvent can be present in the additive concentrate composition at 0 to 99 percent by weight, and in other instances at 3 to 80 percent by weight, or 10 to 70 percent by weight.
• the friction modifier of the present invention and the additional performance additives taken separately or in combination can be present in the additive concentrate composition at 0.01 to 100 percent by weight, and in other instances can be present at 0.01 to 95 percent by weight, at 0.01 to 90 percent by weight, or at 0.1 to 80 percent by weight.
• the additive concentrate may comprise the friction modifier of the present invention and be substantially free of any additional solvent.
• the additive concentrate containing the friction modifier of the present invention is neat, in that it does not contain any additional solvent added to improve the material handling characteristics of the concentrate, such as its viscosity.
• the fuel composition, fuel additive concentrate, and/or the friction modifier itself are substantially free of or free of at least one member selected from the group consisting of sulphur, phosphorus, sulfated ash, and combinations thereof, and in other embodiments the fuel composition contains less than 50 ppm, 20 ppm, less than 15 ppm, less than 10 ppm, or less than 1 ppm of any one or all of these members.
• the additive concentrate composition or fuel composition containing the friction modifier of the present invention can be prepared by admixing or mixing the components of the composition at ambient to elevated temperatures usually up to 60° C. until the composition is homogeneous.
• the fuel composition of the present invention comprises the friction modifier described above and a liquid fuel and is useful in fueling an internal combustion engine. Fuel may also be a component on the additive compositions described above.
• the fuel is normally a liquid at ambient conditions e.g., room temperature (20 to 30° C.).
• the liquid fuel can be a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof.
• the hydrocarbon fuel can be a petroleum distillate to include a gasoline as defined by ASTM specification D4814 or a diesel fuel as defined by ASTM specification D975.
• the liquid fuel is a gasoline, and in one embodiment the liquid fuel is a a nonleaded gasoline.
• the liquid fuel is a diesel fuel.
• the hydrocarbon fuel can be a hydrocarbon prepared by a gas to liquid process to include for example hydrocarbons prepared by a process such as the Fischer-Tropsch process.
• the non-hydrocarbon fuel can be an oxygen containing composition, often referred to as an oxygenate, which includes an alcohol, an ether, a ketone, an ester of a carboxylic acid, a nitroalkane, or a mixture thereof.
• the non-hydrocarbon fuel can include for example methanol, ethanol, methyl t-butyl ether, methyl ethyl ketone, transesterified oils and/or fats from plants and animals such as rapeseed methyl ester and soybean methyl ester, and nitromethane.
• liquid fuel is an emulsion of water in a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof.
• the liquid fuel can have a sulphur content on a weight basis that is 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less.
• the liquid fuel of the invention is present in a fuel composition in a major amount that is generally greater than 95% by weight, and in other embodiments is present at greater than 97% by weight, greater than 99.5% by weight, or greater than 99.9% by weight.
• the friction modifier of the present invention may be represented by Formula I, as shown above.
• the friction modifier may also be used as an antioxidant, a rust and/or corrosion inhibitor, an antiwear agent, a demulsifier, or some combination thereof.
• the compound of Formula I contains an imide group.
• the imide group is typically formed by taking together the Y and Y′ groups and forming a R 1 —N ⁇ group between two >C ⁇ O groups.
• the compound of Formula I has m, n, X, and R 1 , R 2 and R 6 defined as follows: m is 0 or 1, n is 1 to 2, X is >CHOR 6 , and R 1 , R 2 and R 6 are independently hydrocarbyl groups containing 4 to 30 carbon atoms.
• Y and Y′ are both —O—.
• the compound of Formula I has m, n, X, Y, Y′ and R 1 , R 2 and R 6 defined as follows: m is 0 or 1, n is 1 to 2, X is >CHOR 6 ; Y and Y′ are both —O—, and R 1 , R 2 and R 6 are independently hydrogen or hydrocarbyl groups containing 4 to 30 carbon atoms.
• the friction modifier includes imides, di-esters, di-amides, di-imides, ester-amides, ester-imides, or imide-amides. In one embodiment the friction modifier includes imides, di-esters, di-amides, or ester-amides.
• the di-esters, di-amides, ester-amide, ester-imide compounds of Formula I may be prepared by reacting a dicarboxylic acid (such as tartaric acid), with an amine or alcohol, optionally in the presence of a known esterification catalyst.
• a dicarboxylic acid such as tartaric acid
• an amine or alcohol optionally in the presence of a known esterification catalyst.
• ester-imide compounds it is necessary to have at least three carboxylic acid groups (such as citric acid).
• a di-imide it is necessary to have at least four carboxylic acid groups.
• the amine or alcohol typically has sufficient carbon atoms to fulfill the requirements of R 1 and/or R 2 as defined in Formula I.
• R 1 and R 2 are independently linear or branched hydrocarbyl groups. In one embodiment the hydrocarbyl groups are branched. In one embodiment the hydrocarbyl groups are linear.
• the R 1 and R 2 may be incorporated into Formula I by either an amine or an alcohol.
• the alcohol includes both monohydric alcohol and polyhydric alcohol.
• the carbon atoms of the alcohol may be linear chains, branched chains, or mixtures thereof.
• branched alcohol examples include 2-ethylhexanol, isotridecanol, Guerbet alcohols, or mixtures thereof.
• Examples of a monohydric alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, or mixtures thereof.
• the monohydric alcohol contains 5 to 20 carbon atoms.
• the alcohol includes either a monohydric alcohol or a polyhydric alcohol.
• suitable polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,5-pentane diol, 1,6-hexane diol, glycerol, sorbitol, pentaerythritol, trimethylolpropane, starch, glucose, sucrose, methylglucoside, or mixtures thereof.
• the polyhydric alcohol is used in a mixture along with a monohydric alcohol. Typically, in such a combination the monohydric alcohol constitutes at least 60 mole percent, or at least 90 mole percent of the mixture.
• the friction modifier is derived from tartaric acid.
• the tartaric acid used for preparing the tartrates of the invention can be commercially available, and it is likely to exist in one or more isomeric forms such as d-tartaric acid, l-tartaric acid, d,l-tartaric acid or mesotartaric acid, often depending on the source (natural) or method of synthesis (from maleic acid).
• a racemic mixture of d-tartaric acid and l-tartaric acid is obtained from a catalysed oxidation of maleic acid with hydrogen peroxide (with tungstic acid catalyst).
• These derivatives can also be prepared from functional equivalents to the diacid readily apparent to those skilled in the art, such as esters, acid chlorides, or anhydrides.
• the friction modifier includes a compound derived from a hydroxycarboxylic acid.
• the friction modifier is derived from at least one of hydroxy-polycarboxylic acid di-ester, a hydroxy-polycarboxylic acid di-amide, a hydroxy-polycarboxylic acid di-imide, a hydroxy-polycarboxylic acid ester-amide, a hydroxy-polycarboxylic acid ester-imide, and a hydroxy-polycarboxylic acid imide-amide.
• the friction modifier is derived from at least one of the group consisting of a hydroxy-polycarboxylic acid di-ester, a hydroxy-polycarboxylic acid di-amide, and a hydroxy-polycarboxylic acid ester-amide.
• a suitable a hydroxycarboxylic acid examples include citric acid, tartaric acid, lactic acid, glycolic acid, hydroxy-propionic acid, hydroxyglutaric acid, or mixtures thereof.
• friction modifier is derived from tartaric acid, citric acid, hydroxy-succinic acid, dihydroxy mono-acids, mono-hydroxy diacids, or mixtures thereof.
• the friction modifier includes a compound derived from tartaric acid or citric acid.
• the friction modifier includes a compound derived from tartaric acid.
• the compound of Formula (I) is not a citrate.
• US Patent Application 2005/198894 discloses suitable hydroxycarboxylic acid compounds, and methods of preparing the same.
• Canadian Patent 1183125; US Patent Publication numbers 2006/0183647 and US-2006-0079413; U.S. Patent Application No. 60/867,402; and British Patent 2 105 743 A all disclose examples of suitable tartaric acid derivatives.
• the di-esters, di-amides, di-imides, ester-amide, ester-imide, imide-amide compounds are derived from a compound of Formula I.
• the di-esters, di-amides, ester-amide, compounds are derived from a compound of Formula I.
• the friction modifier includes imide, di-esters, di-amides, ester-amide derivatives of tartaric acid.
• a suitable citric acid derivative examples include trialkyl citrates or borated trialkyl citrates. Suitable examples include triethyl citrate, tripentyl citrate with ethyl dipentyl citrate, borated triethyl citrate, tributyl citrate, triethyl citrate transesterified with 1,2-propandiol, triethyl O-acetyl citrate, triethyl citrate octadecyl succinate, or mixtures thereof.
• suitable citrates is disclosed in WO 2005/087904 and U.S. Pat. No. 5,338,470.
• Other suitable citrates include 2-ethylhexyl citrate, dodecyl citrate, or mixtures thereof.
• the friction modifier of the invention may also function as a rust and/or corrosion inhibitor, an antiwear agent, and/or a demulsifier.
• the friction modifier is not borated.
• the friction modifier is the condensation product derived from the reaction of component (a)(i), which is made up of certain carboxylic acids, and component (a)(ii), a mixture comprising one or more branched alcohols or branched amines where the alcohols and/or amine each contain from 1 to about 150 carbon atoms.
• This condensation product acts as a friction modifier and/or antiwear agent in the fuel compositions of the present invention.
• the friction modifier of the present invention may be prepared conveniently by reacting one or more of the carboxylic acids described either above or below with one or more of the branched alcohols and/or branched amines described either above or below by a well-known condensation process.
• components (a)(i) and (a)(ii) are reacted in a 1:0.5-2 molar ratio wherein the ratio represents moles of reactive carboxylic acid functional groups in (a)(i) to moles of active hydroxyl groups in (a)(ii).
• the ratio is a 1:0.5-1 molar ratio, and in some embodiments, the ratio is a 1:1 molar ratio.
• the friction modifiers of the present invention can be solids, semi-solids, or liquids (oils) depending on the particular alcohol(s) and/or amine(s) used in preparing them.
• the friction modifiers are advantageously soluble and/or stably dispersible in such oleaginous compositions.
• compositions intended for use in fuels are typically fuel-soluble and/or stably dispersible in a fuel in which they are to be used.
• fuel-soluble as used in this specification and appended claims does not necessarily mean that all the compositions in question are miscible or soluble in all proportions in all fuels.
• composition is soluble in a fuel (hydrocarbon, non-hydrocarbon, mixtures, etc) in which it is intended to function to an extent which permits the solution to exhibit one or more of the desired properties.
• a fuel hydrocarbon, non-hydrocarbon, mixtures, etc
• solutions it is not necessary that such “solutions” be true solutions in the strict physical or chemical sense. They may instead be micro-emulsions or colloidal dispersions which, for the purpose of this invention, exhibit properties sufficiently close to those of true solutions to be, for practical purposes, interchangeable with them within the context of this invention.
• the friction modifiers of this invention are useful as additives for fuels, in which they may function not only as friction modifiers but also as rust and/or corrosion inhibitors, antiwear agents, and/or demulsifiers.
• the friction modifier of the present invention can be present in fuel compositions at 1 to 10,000 ppm (where ppm is calculated on a weight:weight basis).
• the friction modifier is present in fuel compositions in ranges with lower limits of 1, 3, 5, 10, 50, 100, 150 and 200 ppm and upper limits of 10,000, 7,500, 5,000, and 2,500 where any upper limit may be combined with any lower limit to provide a range friction modifier present in the fuel compositions.
• Component (a)(i) is made up of one or more carboxylic acids where the acid is described by Formula II shown above.
• component (a)(i) is made up of one or more dicarboxylic acids where the acid is described by the following formula:
• each X is independently —Z—O—Z—, >CH 2 , >CR 1 R 2 , >C(OH)(CO 2 R 2 ), or >CHOR 2 ; and wherein each Z is independently >CH 2 , >CR 1 R 2 , >C(OH)(CO 2 R 2 ), or >CHOR 2 ;
• m is 0 or 1;
• the X in formula I and/or formula Ia is >CHOR 2 and n is 2.
• (X) n in formula I and/or formula Ia is —CH 2 —C(OH)(CO 2 R 2 )—CH 2 —.
• component (a)(i) is tartaric acid, citric acid, derivatives and/or functional equivalents of either acid, or combinations thereof.
• component (a)(i) is represented by either Formula III:
• each R 3 is independently H, or a hydrocarbyl group, or wherein the R 3 groups together form a ring; or Formula IV:
• each R 3 is independently H, or a hydrocarbyl group; or combinations thereof.
• the acid used in the present invention includes tartaric acid
• the acid can be the commercially available type (obtained from Sargent Welch), and it is likely to exist in one or more isomeric forms such as d-tartaric acid, l-tartaric acid, d,l-tartaric acid, or mesotartaric acid, often depending on the source (natural) or method of synthesis (e.g. from maleic acid).
• These derivatives can also be prepared from functional equivalents to the diacid readily apparent to those skilled in the art, such as esters, acid chlorides, anhydrides, etc. Similar characteristics apply to the citric acid and other acids which may be used in the present invention, including but not limited to the fact that isomers may be present in the acid source and that functional equivalents of the acids may be used.
• Component (a)(ii) is made up of one or more branched alcohols, one or more branched amines, or combinations thereof.
• the alcohols and amines suitable for use in the invention are branched as opposed to linear in structure.
• all, or substantially all, of the alcohols and/or amines that make up component (a)(ii) are branched. It is understood that industrial sources of some alcohols and amines contain ranges of structures and configurations and that while, for example, an alcohol source may be identified as a branched structure, the source may contain some small amount of linear alcohols and even small amounts of linear and branched alcohols other than the primary identify given.
• the alcohols and/or amines that make up component (a)(ii) are ⁇ 25 or >25 percent by weight branched in structure, or are ⁇ 50 or >50 percent by weight branched in structure, or are ⁇ 75 or >75 percent by weight branched in structure, or are ⁇ 90 or >90 percent by weight branched in structure.
• component (a)(ii) is more than 95 percent by weight branched.
• the amines suitable for use in the invention may have the formula RR′NH wherein R and R′ each independently represent H or a branched hydrocarbon-based radical of from 1 to 150, or from 1 to 30 or from 6 to 16, or from 6 to 150, or from 8 to 150 carbon atoms.
• R and R′ each independently represent H or a branched hydrocarbon-based radical of from 1 to 75, or from 1 to 15 or from 3 to 8, or from 3 to 75, or from 4 to 75 carbon atoms with the proviso that the total number of carbon atoms in R and R′ combined is from 1 to 150, or from 1 to 30, or from 8 to 16, or from 6 to 150, or from 8 to 150 carbon atoms.
• the total number of carbon atoms in R and R′ combined is from 6 to 16.
• the amines may be branched at any point in the chain of each hydrocarbon-based radical and the branching may be of any length.
• amines may be employed either alone or in combination with the amines described above wherein the amines are characterized by the ranges of the number of carbon atoms present in the amine, where the ranges have a lower carbon number of 2, 3, 4, 6, 10, or 12 carbon atoms and an upper carbon number of 120, 80, 48, 24, 20, 18, or 16 carbon atoms.
• each of the groups R and R′ has 8 to 30 carbon atoms.
• the sum of carbon atoms in R and R′ is at least 8.
• R and R′ may also be —R′′OR′′′ in which R′′ is a divalent alkylene radical of 2 to 6 carbon atoms and R′′′ is a hydrocarbyl radical of 5 to 150 or to 148 or to 146 or to 144 carbon atoms.
• the amines suitable for the present invention include those represented by the formula RR′NH wherein R and R′ represent H or a hydrocarbyl radical of 1 to 150 carbon atoms provided that the sum of the carbon atoms in R and R′ is at least 6.
• R or R′ contain 6 to 16 carbons and in another embodiment from 8 to 13 carbon atoms, and in yet another embodiment 8 carbon atoms
• the alcohols useful for preparing the friction modifier are branched alcohols and similarly contain from 1 to 150, or from 1 to 30 or from 6 to 16, or from 6 to 150, or from 8 to 150 carbon atoms. In one set of embodiments, the alcohols may contain the same ranges of total number of carbon atoms as described above for the amines.
• the alcohols may be branched at any point in the chain and the branching may be of any length.
• component (a)(ii) contains one or more alcohols selected from the following group: 2-methyl-1-pentanol, 2-ethylhexanol, 2-octanol, isooctyl alcohol, isotridecyl alcohol, or combinations thereof.
• the specific alcohols described above are used in combination with dicarboxylic acids, wherein the dicarboxylic acids are tartaric acid, citric acid or combinations thereof.
• alcohols suitable for use in the present invention contain from 6 to 150 carbon atoms and in some embodiments from 6 to 16 carbon atoms. In other embodiments the alcohols used in the present invention contain from 8 to 150 carbon atoms or from 8 to 16 carbon atoms. In still other embodiments the alcohols contain 8 to 10 carbon atoms or 8 carbon atoms.
• the alcohols are characterized by the ranges of the number of carbon atoms present in the alcohol, where the ranges have a lower carbon number of 2, 3, 4, 6, 8, 10, or 13 carbon atoms and an upper carbon number of 120, 80, 48, 24, 20, 18, 16, or 13 carbon atoms.
• component (a)(ii) includes one or more branches alcohols and/or amines wherein the branching occurs in the number two position.
• the alcohols and/or amines are iso structured.
• the alcohols and/or amines contain at least one branched group where the branched group is a methyl group or an ethyl group.
• the alcohols and/or amines contain one branched group where the branched group is a methyl group or an ethyl group.
• the alcohols and/or amines that make up component (a)(ii) are ⁇ 25 or >25 percent by weight branched in structure and contain from 6 or 8 to 13 carbon atoms. In other embodiments the alcohols are ⁇ 50 or >50 percent by weight branched in structure and contain either from 6 or 8 to 13 carbon atoms. In still other embodiments the alcohols are >95 percent by weight branched in structure and contain either from 6 or 8 to 13 carbon atoms.
• the additive compositions and fuel compositions of the present invention can further comprise one or more additional performance additives.
• Additional performance additives can be added to a fuel composition depending on several factors to include the type of internal combustion engine and the type of fuel being used in that engine, the quality of the fuel, and the service conditions under which the engine is being operated.
• the additional performance additives can include an antioxidant such as a hindered phenol or derivative thereof and/or a diarylamine or derivative thereof, a corrosion inhibitor such as an alkenylsuccinic acid, and/or a detergent/dispersant additive such as a polyetheramine or nitrogen containing detergent, including but not limited to PIB amine dispersants, quaternary salt dispersants, and succinimide dispersants.
• the additional performance additives may also include a cold flow improver such as an esterified copolymer of maleic anhydride and styrene and/or a copolymer of ethylene and vinyl acetate, a foam inhibitor such as a silicone fluid, a demulsifier such as a polyalkoxylated alcohol, a lubricity agent such as a fatty carboxylic acid, a metal deactivator such as an aromatic triazole or derivative thereof, a valve seat recession additive such as an alkali metal sulfosuccinate salt, a biocide, an antistatic agent, a deicer, a fluidizer such as a mineral oil and/or a poly(alpha-olefin) and/or a polyether, and a combustion improver such as an octane or cetane improver.
• a cold flow improver such as an esterified copolymer of maleic anhydride and styrene and/or a copolymer
• the additional performance additives can each be added directly to a additive and/or fuel compositions of the present invention, but they are generally added together in an additive concentrate composition to a fuel composition with the friction modifier of the present invention.
• the additive concentrate composition is described in more detail above.
• the invention is useful for a liquid fuel and/or for an internal combustion engine, including either compression ignition engines or spark ignited engines.
• the internal combustion engine includes 2-stroke or 4-stroke engines fuelled with gasoline, diesel, a natural gas, a mixed gasoline/alcohol or any of the fuels described in the sections above.
• the compression ignition engines include both light duty and heavy duty diesel engines.
• the spark ignited engines include direct injection gasoline engines.
• the invention is useful in additive compositions in that the friction modifier described above provides improve low temperature storage stability and so improved handling properties for the friction modifier itself and additive compositions and/or concentrates containing the friction modifier.
• the additive compositions of the present invention may be used in a lubricating composition such that the additives are present in the lubricating system of the engine.
• the additives may also enter the combustion chamber of the engine during operation of the engine by the transfer of small amounts of the additive containing lubricating composition to the combustion chamber due to a phenomenon referred to as “blow by” where the lubricating composition, and in this case the additive composition, pass around the piston heads inside the cylinder, moving from the lubricating system of the engine into the combustion chamber.
• hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
• hydrocarbyl groups include: hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention
• Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
• substituents as pyridyl, furyl, thienyl and imidazolyl.
• no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.
• Samples of friction modifiers including the friction modifiers of the present invention are tested to evaluate their low temperature storage stability characteristics.
• Samples of the friction modifiers are tested neat, with no other components present in the sample, and in blends, where the friction modifiers are mixed with one or more solvents to give results representative of a fuel concentrate or fuel composition containing the friction modifiers.
• sample bottles are filled approximately 2 ⁇ 3 full with sample materials, typically requiring about 50 ml for each test sample.
• Each sample is stored for four weeks at three different temperatures, with a separate sample set prepared for each temperature tested.
• the neat samples and the blend samples are rated after 3 weeks and 4 weeks of storage.
• one set of neat samples is stored at 0° C. and one set at ⁇ 18° C.
• one set of blend samples is stored at 0° C., one set at ⁇ 8° C., and one set at ⁇ 18° C.
• Table below summarizes the examples:
• Blend Components and Formulation Example ID Friction Modifier Solvent(s) Formulation in PBW 1 Comp 1B Comp 1 Xylene:Isobutanol:Amyl Alcohol 30:35:17.5:17.5
• 2B Comp 2 Xylene:Isobutanol:Amyl Alcohol 30:35:17.5:17.5
• 3B Comp 3 Xylene:Isobutanol:Amyl Alcohol 30:35:17.5:17.5
• 4B Comp 4 Xylene:Isobutanol:Amyl Alcohol 30:35:17.5:17.5
• 5B Comp 5 Xylene:Isobutanol:Amyl Alcohol 30:35:17.5:17.5
• 6B Comp 6 Xylene:Isobutanol:Amyl Alcohol 30:35:17.5:17.5
• 7B Comp 7 Xylene:Isobutanol:Amyl Alcohol 30:35:17.5:17.5
• 8B Comp
• Comp 1B with a formulation shown as 30:35:17.5:17.5 is 30 pbw friction modifier, 35 pbw xylene, 17.5 pbw isobutanol and 17.5 pbw amyl alcohol.
• each sample is rated for its clarity, the presence of any sediment, and the presence of any gel. Other observations on the sample are also taken. Abbreviations are used in the rating process and results are reported in the following order: Clarity Sediment/Gel/Special Cases. If one or more category above is left blank, then it is to be understood that nothing was observed under that category.
• the table below summarizes the rating abbreviations used in the testing, with the various ratings given in each category from good to bad and/or better to worse, with the caveat that no rating in the sediment, gel or special case categories, meaning no sediment, gel or special case is present, is preferred.
• the best possible rating a sample could receive is “C” meaning the sample is clear and there is no sediment, gel or special case present.

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• 2009
  • 2009-07-07 EP EP09790091A patent/EP2324101A1/en not_active Withdrawn
  • 2009-07-07 CN CN2009801269099A patent/CN102089410A/zh active Pending
  • 2009-07-07 KR KR1020117003080A patent/KR20110026524A/ko not_active Application Discontinuation
  • 2009-07-07 WO PCT/US2009/049739 patent/WO2010005921A1/en active Application Filing
  • 2009-07-07 US US13/000,095 patent/US20110162263A1/en not_active Abandoned
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