EP2611892A2 - Functionalized maleated fatty acids as non acidic fluid additives - Google Patents
Functionalized maleated fatty acids as non acidic fluid additivesInfo
- Publication number
- EP2611892A2 EP2611892A2 EP11822341.1A EP11822341A EP2611892A2 EP 2611892 A2 EP2611892 A2 EP 2611892A2 EP 11822341 A EP11822341 A EP 11822341A EP 2611892 A2 EP2611892 A2 EP 2611892A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- fatty acid
- group
- acid
- unsaturated
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- 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
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- 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
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- 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
- C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
-
- 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
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- 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
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/72—Esters of polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/16—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
- C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to methods and compositions for improving the properties of various fluids, and more particularly relates, in one non-limiting embodiment, to methods and compositions for hydrocarbon fuel lubricity additives made from maleic anhydride and fatty acids.
- the fatty acids, fatty acid ammonium salts and fatty acid amides either have to be greatly diluted or kept in heated storage vessels and added via heated pipework.
- a method of improving the lubricity of a hydrocarbon fuel involves adding to the hydrocarbon fuel an effective amount of functionalized maleated fatty acid that is an ester, imide and/or amide to improve the lubricity thereof.
- the functionalized maleated fatty acid is made by a process including reacting an unsaturated fatty acid with an unsaturated compound selected from the group consisting of an unsaturated anhydride, a maleimide, and mixtures thereof.
- the unsaturated compound may be substituted with a linear or branched alkyl group. This first step gives a maleated fatty acid.
- the maleated fatty acid is reacted with a multifunctional reactant selected from the group consisting of a polyol, an alkanolamine, an alkylene oxide and mixtures thereof.
- a multifunctional reactant selected from the group consisting of a polyol, an alkanolamine, an alkylene oxide and mixtures thereof.
- the functionalized maleated fatty acid may optionally have one of the structures (I) through (IX) shown below.
- the functional- ized maleated fatty acid may also improve the lubricity of a lubricant, e.g. a motor oil; a transmission fluid, e.g. in an automotive automatic transmission, and in an alcohol, e.g. in methanol and/or ethanol when used as a fuel. Further, it is expected that the functionalized maleated fatty acid may also reduce the corrosivity of these fluids with respect to metals that they come into contact with, as well as to reduce the corrosivity of hydrocarbon fuels.
- a lubricant e.g. a motor oil
- a transmission fluid e.g. in an automotive automatic transmission
- an alcohol e.g. in methanol and/or ethanol
- functionalized maleated fatty acids which may be esters, imides and/or amides, may improve the properties of certain fluids; for instance they may improve the lubricity and the corrosivity of fuels and lubricants, such as hydrocarbon and/or alcohol fuels and lubricants.
- Maleated fatty acids are produced through the reaction of unsaturated fatty acids, such as oleic acid or linoleic acid with maleic anhydride.
- the resulting maleated fatty acids may be further functionalized with a polyol, e.g. ethylene glycol, glycerol and the like, to make a non-acidic triester; with an alkanolamine to make an imide/amide hybrid; and with an alkanolamine and polyols to make an imide/ester hybrid.
- the triester, or amide/ester hybrid are more readily made by alkoxylation with alkanolamine, ethylene oxide (EO) and/or propylene oxide (PO).
- the functionalized maleated fatty acid may have a structure of a formula selected from the group (I) through (IX) consisting of:
- R 2 is a direct bond or hydrocarbyl group having 1 to 1 0 carbons with one or more double bonds
- R 3 is - (CH 2 CH 2 0) n -, or -(CH 2 CH(CH 3 )0) n -, or combinations thereof,
- R 4 is -(CH 2 CH 2 0) n H, -(CH 2 CH(CH 3 )0) n H, -CH 2 CHOHCH 2 OH, or
- n is an integer from 1 to 1 0, alternatively from 1 to 5.
- the functionalized maleated fatty acids herein in one useful, non- limiting embodiment may be essentially non-acidic, due to all of the carboxylic acid groups being reacted or functionalized, with a multifunctional reactant.
- the acid number of the functionalized maleated fatty acids is less than 1 0, in another non-limiting embodiment the acid number is less than 5; alternatively it is less than 3. Because these materials are essentially non-acidic or have very low acidity, their ability to contribute to deposit formation tendency of the fluid (e.g. fuel) to which they are added is greatly reduced, and as noted, in some contexts may serve as corrosion inhibitors.
- the unsaturated fatty acid used to make the additives described herein may have a weight average molecular weight between about 300 to about 5000 and may be selected from the group consisting of monomeric, dimeric, trimeric crosslinked unsaturated fatty acids, unsaturated fatty acids having from 2 to 30 carbon atoms and mixtures thereof. Specific examples include, but are not necessarily limited to oleic acid, linoleic acid, a-linolenic acid, C1 0 to C40 unsaturated synthetic dimer fatty acids, unsaturated fatty acids having from 2 to 30 carbon atoms, such as those obtained from the olefin metathesis of fatty acids, arachidonic acid, and mixtures thereof.
- the unsaturated compound that is initially reacted with the unsaturated fatty acid is an unsaturated anhydride, such as maleic anhydride or phthalic anhydride; a maleimide, such as maleimide itself or other maleimide, or mixtures thereof.
- unsaturated anhydride such as maleic anhydride or phthalic anhydride
- maleimide such as maleimide itself or other maleimide, or mixtures thereof.
- reactants may be substituted with a linear or branched alkyl group, in one embodiment a lower alkyl group, which is defined herein as having from 1 to 4 carbon atoms.
- the molar ratio of unsaturated fatty acid to unsaturated compound ranges from about 1 :50 independently to about 50: 1 in one non-limiting embodiment, in another aspect from about 1 :1 0 independently to about 10:1 , alternatively from about 1 :2 independently to about 2:1 or in another non-restrictive version from about 1 .1 :1 independently to about 1 :1 .1 or equimolar.
- independently it is meant than any of the lower thresholds may be combined with any of the upper thresholds.
- the multifunctional reactants that are reacted with the maleated fatty acid include, but are not necessarily limited to, polyols, alkanolamines, alkylene oxides and mixtures thereof.
- Suitable polyols include, but are not necessarily limited to glycol, e.g. ethylene glycol and other glycols for instance propylene glycol; glycerol; alkyl phenols; alkyoxylated alkyl phenol; linear or branched alkyl alcohols; each of which may have from 2 to 30 carbon atoms and mixtures thereof.
- Suitable alkanolamines include, but are not necessarily limited to, ethanolamine, propanolamine, diethanolamine, n-alkylethanolamine, isopropanol amine, diisopropanol amine, 3-amino-1 ,2-propanediol and mixtures thereof.
- Suitable alkylene oxides include, but are not necessarily limited to, ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
- the molar ratio of maleated fatty acid to multifunctional reactant ranges from about 1 :20 to about 20:1 may range from about 1 :20 independently to about 20:1 ; alternatively from about 10:1 independently to about 1 :10.
- the reactions to make the functionalized maleated fatty acids proceed well without special considerations and are known to those skilled in the art. In general, they may proceed at a temperature range between about 160 to about 260 °C and a pressure range between about 1 to about 10 atm (0.1 to 1 MPa) in the presence of common phenol based antioxidants such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydro- quinone, polyisobutylene phenol, tocopherol (Vitamin E family) and the like and mixtures thereof.
- Lewis acid catalysts may be used to improve the reaction rate, but no catalysts are generally used.
- distillate fuels include, but are not necessarily limited to diesel fuel, kerosene, gasoline middle distillate fuel, and the like. They may also be used in heavy fuel oil. It will be appreciated that distillate fuels include blends of conventional hydrocarbons meant by these terms with oxygenates, e.g. alcohols, such as methanol, ethanol, and other additives or blending components presently used in these distillate fuels, or that may be used in the future.
- oxygenates e.g. alcohols, such as methanol, ethanol, and other additives or blending components presently used in these distillate fuels, or that may be used in the future.
- the methods and compositions herein relate to low sulfur fuels, which are defined as having a sulfur content of 0.2% by weight or less, and in another non-limiting embodiment as having a sulfur content of about 0.0015 wt.% or less - such as the so-called "ultra low sulfur" fuels.
- hydrocarbon fuels herein include, but are not necessarily limited to, diesel and kerosene, and in one non-restrictive version, ultra low sulfur diesel (ULSD) fuels. However, they also may be used for fuels having sulfur contents higher than this.
- ULSD ultra low sulfur diesel
- the functionalized maleated fatty acids described herein may also be used as corrosivity improvers for the fuels described above, for instance when these fuels come into contact with metal, particularly, but not limited to, iron alloys, particularly the various commonly used steel alloys.
- the functionalized maleated fatty acids may function as corrosion inhibitors or lubricity enhancers in other fluids including, but not necessarily limited to, lubricants, such as motor oil, transmission fluids, cutting fluids, and the like.
- the lubricity additive in the total fuel should at least be an amount to improve the lubricity of the fuel as compared to an identical fuel absent the additive.
- the amount of additive may range from about 25 independently to about 3000 ppm, and in an alternate embodiment, the lower threshold may be about 25 ppm and the upper threshold may independently be about 200 ppm and in one non-limiting embodiment from about 50 independently to about 150 ppm.
- the amount of additive should be that effective to reduce the corrosivity of the fluid as compared to an identical fuel absent the additive. In one non-limiting embodiment, the amount may range from about 1 independently to about 1 00 ppm, alternatively from about 1 independently to about 1 0 ppm.
- optional components may be added independently to the fluids being treated.
- these may include, but are not necessarily limited to, detergents, pour point depressants, cetane improvers, dehazers, cold operability additives (e.g. cold flow improvers), conductivity improvers, other corrosion inhibitors, stability additives, demulsifiers, biocides, dyes, and mixtures thereof.
- water is explicitly absent from the inventive composition.
- maleated fatty acid In a typical reaction, oleic acid (1 00 g) and maleic anhydride (25 g) were charged into a 250 ml 3-neck flask under nitrogen. The mixture was heated sequentially up to 240 °C for 30 hrs until the reaction was completed. The reaction was monitored by FT- infrared spectroscopy (FT-I R) as is known to those skilled in the art. The final product was diluted by aromatic solvent to a concentration of 90% active and marked as Example 1 .
- FT-I R FT- infrared spectroscopy
- Example 1 material Above is a representative structure of Example 1 material.
- Oleic acid (100.1 g) and maleic anhydride (25.3 g) were mixed in a 3-neck flask. The mixture was heated sequentially up to 240 °C until the reaction is completed as monitored by FT-I R. The reaction mixture was first cooled to room temperature, and then ethanolamine (38.0 g) was added drop- wise while stirring. After the addition was completed, the reaction temperature was first set at 80 °C, and then raised to 180 °C sequentially in 2 hours. The reaction process was monitored by FT-IR and acid number analysis. A second batch of ethanolamine (6.0 g) was added after 8 hrs reaction time. The reaction was stopped when the acid number is below 3. The final product was diluted with aromatic solvent to a concentration of 80% active and marked as Example 2.
- Linoleic and oleic acid mixture (100.0 g) and maleic anhydride (25.0 g) were mixed in a 3-neck flask. The mixture was heated sequentially up to 240 °C until the reaction is completed as monitored by FT-IR. The reaction mixture was first cooled to room temperature, and then ethanolamine (15.6 g) was added dropwise while stirring. After the addition was completed, the reaction temperature was first set at 70 °C, and then raised to 1 20 °C sequentially in 4 hours. The reaction process was monitored by FT-I R. Ethylene glycol (22.1 g) was added after the amines are consumed. The temperature was raised to 185 °C and water was removed as a by-product via a Dean-Stark trap. After the acid number reached 20, a second batch of ethylene glycol (4.6 g) was added to drive the acid number further down. The reaction was stopped when the acid number was below 5. The final product was diluted with aromatic solvent to a concentration of 90% active and marked as Example 3.
- Example 5 Above is a representative structure of Example 4.
- Example 5
- the present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed.
- the method may consist essentially of or consist of reacting an unsaturated fatty acid with an unsaturated compound selected from the group consisting of an unsaturated anhydride, a maleimide, and mixtures thereof where the unsaturated compound may be substituted with a linear or branched alkyl group, which reacting gives a maleated fatty acid.
- the method may optionally additionally consist essentially of or consist of reacting the maleated fatty acid with a multifunctional reactant selected from the group consisting of a polyol, an alkanolamine, an alkylene oxide and mixtures thereof to give a functionalized maleated fatty acid that has an acid number less than 10, where the reactants are as described in the claims.
- a multifunctional reactant selected from the group consisting of a polyol, an alkanolamine, an alkylene oxide and mixtures thereof to give a functionalized maleated fatty acid that has an acid number less than 10, where the reactants are as described in the claims.
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
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Abstract
Maleated fatty acids that are functionalized with materials such as polyols, alkanolamines and/or alkylene oxides have been discovered to improve the properties of various fluids. In a non-limiting example, functionalized maleated fatty acids having acid numbers less than 10 may improve the lubricity of fuels and lubricants, such as hydrocarbon fuels and lubricants, when added thereto.
Description
FUNCTIONALIZED MALEATED FATTY
ACIDS AS NON ACIDIC FLUID ADDITIVES
INVENTORS: YANG, Jianzhong; BIGGERSTAFF, Paul J.;
and WEERS, Jerry J.
TECHNICAL FIELD
[0001] The present invention relates to methods and compositions for improving the properties of various fluids, and more particularly relates, in one non-limiting embodiment, to methods and compositions for hydrocarbon fuel lubricity additives made from maleic anhydride and fatty acids.
TECHNICAL BACKGROUND
[0002] It is well known that in many internal combustion engines the fuel is also the lubricant for the fuel system components, such as fuel pumps and injectors. Many studies of fuels with poor lubricity have been conducted in an effort to understand fuel compositions that have poor lubricity and to correlate lab test methods with actual field use. The problem is general to diesel fuels, kerosene and gasolines, however, most of the studies have concentrated on the first two hydrocarbon fuels.
[0003] Previous work has shown that saturated, monomeric and dimeric, fatty acids of from 12 to 54 carbon atoms used individually give excellent performance as fuel lubricity aids in diesel fuels. A number of other kinds of lubricity additives are also known. Since the advent of low sulfur diesel fuels in the early 1 990s, relatively large amounts of these lubricity additives have been used to provide a fuel that does not cause excessive wear of engine parts.
[0004] Unfortunately, many commercially available fatty acids and fatty acid blends tend to freeze or form crystals at lower temperatures common during winter weather. The freezing or formation of crystals makes handling of the additives, and particularly their injection into fuel, difficult. Blending the fatty acid with a solvent can lower the freezing point and reduce the crystal formation temperature, or cloud point. However, addition of a solvent may increase cost and preparation complexity.
[0005] Some of the fatty acids, fatty acid ammonium salts and fatty acid amides presently used may have the disadvantage of solidifying on storage at low temperatures. Often even at room temperature, crystalline fractions may separate and cause handling problems. Diluting the additives with organic solvents only partly solves the problem, since fractions may still crystallize out from solutions or the solution may gel and solidify. Thus, for use as lubricity additives, the fatty acids, fatty acid ammonium salts and fatty acid amides either have to be greatly diluted or kept in heated storage vessels and added via heated pipework.
[0006] Thus, it would be desirable if a way could be discovered to enhance the lubricity of distillate fuels, but the fuels remain homogeneous, clear and flowable at low temperatures. Further, the cold flow properties of middle distillate fuels with the additives should not be significantly adversely affected.
SUMMARY
[0007] There is provided, in one non-limiting form, a method of improving the lubricity of a hydrocarbon fuel that involves adding to the hydrocarbon fuel an effective amount of functionalized maleated fatty acid that is an ester, imide and/or amide to improve the lubricity thereof. The functionalized maleated fatty acid is made by a process including reacting an unsaturated fatty acid with an unsaturated compound selected from the group consisting of an unsaturated anhydride, a maleimide, and mixtures thereof. The unsaturated compound may be substituted with a linear or branched alkyl group. This first step gives a maleated fatty acid. Subsequently, the maleated fatty acid is reacted with a multifunctional reactant selected from the group consisting of a polyol, an alkanolamine, an alkylene oxide and mixtures thereof. This gives a functionalized maleated fatty acid that has an acid number less than 1 0. The functionalized maleated fatty acid may optionally have one of the structures (I) through (IX) shown below.
[0008] In addition to, or alternative to the above-noted method for improving the lubricity of a hydrocarbon fuel, it is expected that the functional-
ized maleated fatty acid may also improve the lubricity of a lubricant, e.g. a motor oil; a transmission fluid, e.g. in an automotive automatic transmission, and in an alcohol, e.g. in methanol and/or ethanol when used as a fuel. Further, it is expected that the functionalized maleated fatty acid may also reduce the corrosivity of these fluids with respect to metals that they come into contact with, as well as to reduce the corrosivity of hydrocarbon fuels.
DETAILED DESCRIPTION
[0009] It has been discovered that functionalized maleated fatty acids, which may be esters, imides and/or amides, may improve the properties of certain fluids; for instance they may improve the lubricity and the corrosivity of fuels and lubricants, such as hydrocarbon and/or alcohol fuels and lubricants.
[0010] Maleated fatty acids are produced through the reaction of unsaturated fatty acids, such as oleic acid or linoleic acid with maleic anhydride. The resulting maleated fatty acids may be further functionalized with a polyol, e.g. ethylene glycol, glycerol and the like, to make a non-acidic triester; with an alkanolamine to make an imide/amide hybrid; and with an alkanolamine and polyols to make an imide/ester hybrid. The triester, or amide/ester hybrid, are more readily made by alkoxylation with alkanolamine, ethylene oxide (EO) and/or propylene oxide (PO).
[0011] The functionalized maleated fatty acid may have a structure of a formula selected from the group (I) through (IX) consisting of:
re:
or a hydrocarbyl group having 1 to 10 carbon atoms with zero, one or more double bonds,
R2 is a direct bond or hydrocarbyl group having 1 to 1 0 carbons with one or more double bonds,
R3 is - (CH2CH20)n-, or -(CH2CH(CH3)0)n-, or combinations thereof,
R4 is -(CH2CH20)nH, -(CH2CH(CH3)0)nH, -CH2CHOHCH2OH, or
-CH2CH2CH2CH2OH or combinations thereof, and
n is an integer from 1 to 1 0, alternatively from 1 to 5.
[0013] The functionalized maleated fatty acids herein in one useful, non- limiting embodiment, may be essentially non-acidic, due to all of the carboxylic acid groups being reacted or functionalized, with a multifunctional reactant. In an alternate definition, the acid number of the functionalized maleated fatty acids is less than 1 0, in another non-limiting embodiment the acid number is less than 5; alternatively it is less than 3. Because these materials are essentially non-acidic or have very low acidity, their ability to contribute to deposit formation tendency of the fluid (e.g. fuel) to which they are added is greatly reduced, and as noted, in some contexts may serve as corrosion inhibitors.
[0014] The unsaturated fatty acid used to make the additives described herein may have a weight average molecular weight between about 300 to about 5000 and may be selected from the group consisting of monomeric, dimeric, trimeric crosslinked unsaturated fatty acids, unsaturated fatty acids having from 2 to 30 carbon atoms and mixtures thereof. Specific examples include, but are not necessarily limited to oleic acid, linoleic acid, a-linolenic acid, C1 0 to C40 unsaturated synthetic dimer fatty acids, unsaturated fatty acids having from 2 to 30 carbon atoms, such as those obtained from the olefin metathesis of fatty acids, arachidonic acid, and mixtures thereof.
[0015] The unsaturated compound that is initially reacted with the unsaturated fatty acid is an unsaturated anhydride, such as maleic anhydride or phthalic anhydride; a maleimide, such as maleimide itself or other maleimide, or mixtures thereof. These reactants may be substituted with a linear or branched alkyl group, in one embodiment a lower alkyl group, which is defined herein as having from 1 to 4 carbon atoms. The molar ratio of unsaturated fatty acid to unsaturated compound ranges from about 1 :50 independently to about 50: 1 in one non-limiting embodiment, in another aspect from about 1 :1 0
independently to about 10:1 , alternatively from about 1 :2 independently to about 2:1 or in another non-restrictive version from about 1 .1 :1 independently to about 1 :1 .1 or equimolar. By "independently" it is meant than any of the lower thresholds may be combined with any of the upper thresholds.
[0016] The multifunctional reactants that are reacted with the maleated fatty acid include, but are not necessarily limited to, polyols, alkanolamines, alkylene oxides and mixtures thereof. Suitable polyols include, but are not necessarily limited to glycol, e.g. ethylene glycol and other glycols for instance propylene glycol; glycerol; alkyl phenols; alkyoxylated alkyl phenol; linear or branched alkyl alcohols; each of which may have from 2 to 30 carbon atoms and mixtures thereof. Suitable alkanolamines include, but are not necessarily limited to, ethanolamine, propanolamine, diethanolamine, n-alkylethanolamine, isopropanol amine, diisopropanol amine, 3-amino-1 ,2-propanediol and mixtures thereof. Suitable alkylene oxides include, but are not necessarily limited to, ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. The molar ratio of maleated fatty acid to multifunctional reactant ranges from about 1 :20 to about 20:1 may range from about 1 :20 independently to about 20:1 ; alternatively from about 10:1 independently to about 1 :10.
[0017] The reactions to make the functionalized maleated fatty acids proceed well without special considerations and are known to those skilled in the art. In general, they may proceed at a temperature range between about 160 to about 260 °C and a pressure range between about 1 to about 10 atm (0.1 to 1 MPa) in the presence of common phenol based antioxidants such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydro- quinone, polyisobutylene phenol, tocopherol (Vitamin E family) and the like and mixtures thereof. Lewis acid catalysts may be used to improve the reaction rate, but no catalysts are generally used.
[0018] The compositions and methods described herein relate to lubricity additive compositions for distillate fuels, but also may be useful in products from resid. In the context herein, distillate fuels include, but are not necessarily limited to diesel fuel, kerosene, gasoline middle distillate fuel, and the like. They may also be used in heavy fuel oil. It will be appreciated that distillate
fuels include blends of conventional hydrocarbons meant by these terms with oxygenates, e.g. alcohols, such as methanol, ethanol, and other additives or blending components presently used in these distillate fuels, or that may be used in the future. They may also be used in relatively pure alcohols, for instance when an alcohol such as methanol is pumped as a hydrate inhibitor or when ethanol and/or methanol are used as fuels. It is also expected that the functionalized maleated fatty acids will serve as corrosivity preventers and lubricity enhancers in biofuels. In one non-limiting particular embodiment, the methods and compositions herein relate to low sulfur fuels, which are defined as having a sulfur content of 0.2% by weight or less, and in another non-limiting embodiment as having a sulfur content of about 0.0015 wt.% or less - such as the so-called "ultra low sulfur" fuels. Particularly suitable hydrocarbon fuels herein include, but are not necessarily limited to, diesel and kerosene, and in one non-restrictive version, ultra low sulfur diesel (ULSD) fuels. However, they also may be used for fuels having sulfur contents higher than this.
[0019] As previously noted, the functionalized maleated fatty acids described herein may also be used as corrosivity improvers for the fuels described above, for instance when these fuels come into contact with metal, particularly, but not limited to, iron alloys, particularly the various commonly used steel alloys. Besides use as lubricity enhancers and/or corrosivity improvers for the fuels described above, the functionalized maleated fatty acids may function as corrosion inhibitors or lubricity enhancers in other fluids including, but not necessarily limited to, lubricants, such as motor oil, transmission fluids, cutting fluids, and the like.
[0020] In one non-limiting embodiment of the methods and compositions, the lubricity additive in the total fuel should at least be an amount to improve the lubricity of the fuel as compared to an identical fuel absent the additive. Alternatively, the amount of additive may range from about 25 independently to about 3000 ppm, and in an alternate embodiment, the lower threshold may be about 25 ppm and the upper threshold may independently be about 200 ppm and in one non-limiting embodiment from about 50 independently to about 150 ppm.
[0021 ] When the functionalized maleated fatty acid additives are used as corrosion inhibitors, for instance in a hydrocarbon fuel or another fluid as previously described, the amount of additive should be that effective to reduce the corrosivity of the fluid as compared to an identical fuel absent the additive. In one non-limiting embodiment, the amount may range from about 1 independently to about 1 00 ppm, alternatively from about 1 independently to about 1 0 ppm.
[0022] Other, optional components may be added independently to the fluids being treated. In non-limiting embodiments these may include, but are not necessarily limited to, detergents, pour point depressants, cetane improvers, dehazers, cold operability additives (e.g. cold flow improvers), conductivity improvers, other corrosion inhibitors, stability additives, demulsifiers, biocides, dyes, and mixtures thereof. In another non-limiting embodiment of the methods and compositions herein, water is explicitly absent from the inventive composition.
[0023] The invention will now be illustrated with respect to certain Examples which are not intended to limit the invention, but instead to more fully describe it.
EXAMPLES 1 -5
Preparation of Functionalized Maleated Fatty Acid Products
Example 1
[0024] The preparation of maleated fatty acid : In a typical reaction, oleic acid (1 00 g) and maleic anhydride (25 g) were charged into a 250 ml 3-neck flask under nitrogen. The mixture was heated sequentially up to 240 °C for 30 hrs until the reaction was completed. The reaction was monitored by FT- infrared spectroscopy (FT-I R) as is known to those skilled in the art. The final product was diluted by aromatic solvent to a concentration of 90% active and marked as Example 1 .
Above is a representative structure of Example 1 material.
Example 2
[0025] Oleic acid (100.1 g) and maleic anhydride (25.3 g) were mixed in a 3-neck flask. The mixture was heated sequentially up to 240 °C until the reaction is completed as monitored by FT-I R. The reaction mixture was first cooled to room temperature, and then ethanolamine (38.0 g) was added drop- wise while stirring. After the addition was completed, the reaction temperature was first set at 80 °C, and then raised to 180 °C sequentially in 2 hours. The reaction process was monitored by FT-IR and acid number analysis. A second batch of ethanolamine (6.0 g) was added after 8 hrs reaction time. The reaction was stopped when the acid number is below 3. The final product was diluted with aromatic solvent to a concentration of 80% active and marked as Example 2.
Above is a representative structure of Example 2.
Example 3
[0026] Linoleic and oleic acid mixture (100.0 g) and maleic anhydride (25.0 g) were mixed in a 3-neck flask. The mixture was heated sequentially up to 240 °C until the reaction is completed as monitored by FT-IR. The reaction mixture was first cooled to room temperature, and then ethanolamine (15.6 g) was added dropwise while stirring. After the addition was completed, the reaction temperature was first set at 70 °C, and then raised to 1 20 °C sequentially in 4 hours. The reaction process was monitored by FT-I R. Ethylene glycol (22.1 g) was added after the amines are consumed. The temperature was raised to 185 °C and water was removed as a by-product via a Dean-Stark trap. After the acid number reached 20, a second batch of ethylene glycol (4.6 g) was added to drive the acid number further down. The reaction was stopped when the acid number was below 5. The final product was diluted with aromatic solvent to a concentration of 90% active and marked as Example 3.
Above are representative structures of Example 3.
Example 4
[0027] Pre-distilled maleated oleic acid (297.7 g) and ethylene glycol (142.6 g) were charged into a 500 mL 3-neck flask that is equipped with a Dean-Stark trap. The mixtures were heated up to 200 °C to remove water. The reaction process was monitored by FT-I R and acid number. After the acid number reach 20, a second batch of ethylene glycol (6.0 g) was added and heated at 185 °C with N2 purging. The final reaction was stopped when the acid number is less than 10. The final product was collected and marked as Example 4.
Above is a representative structure of Example 4. Example 5
[0028] Pre-distilled maleated oleic acid (224.1 g) and ethylene glycol (36.1 g) were charged into a par reactor. N, N-dimethyl benzylamine (1 .7 g) was added as a base catalyst. The mixture was ethoxylated at 1 1 5 °C till the acid number is less than 2. The final product was collected and marked as Example 5.
Above is a representative structure of Example 5 (Ri = -(CH2CH20)nH, where n = 1 -5).
EXAMPLES 6-1 1
Effectiveness of Ex. 1 -5 Materials as Lubricity Improvers
[0029] The lubricity improvers' effectiveness was examined on a High Frequency Reciprocating Rig (HFRR) in accordance with ASTM D6079. The results are reported in Table I as mean Wear Scar Diameter (WSD) in micrometers. The lower the WSD, the more effective the lubricity improver is. It may be seen that the products from all Examples 1 -5 gave improved lubricity, whereas the material from Example 5 gave the lowest WSD result.
TABLE I
Results of Lubricity Improver Tests
EXAMPLES 12-14
Corrosion Inhibition Results
[0030] The corrosion inhibition property of the above samples was examined with a standard NACE spindle test (TM-01 7201 ) for both gasoline and diesel fuel. The results are reported in a relative scale of A-E with which a rating of "A" means no corrosion while a rating of "E" means more than 75% of the surface is rusted. The results are shown in the Table II.
TABLE II
Corrosion Inhibition Results
[0031] It is to be understood that the invention is not limited to the exact details of monomers, reaction conditions, proportions, etc. shown and described, as modifications and equivalents will be apparent to one skilled in the art. Accordingly, the invention is therefore to be limited only by the scope of the appended claims. Further, the specification is to be regarded in an illustrative rather than a restrictive sense. For example, specific combinations of unsaturated fatty acids, unsaturated compounds, multifunctional reactants, reactant proportions, reaction conditions, molecular weights, dosages and the like falling within the claimed parameters, but not specifically identified or tried in a particular method, are anticipated to be within the scope of this invention.
[0032] The terms "comprises" and "comprising" in the claims should be interpreted to mean including, but not limited to, the recited elements.
[0033] The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. For instance, the method may consist essentially of or consist of reacting an unsaturated fatty acid with an unsaturated compound selected from the group consisting of an unsaturated anhydride, a maleimide, and mixtures thereof where the unsaturated compound may be substituted with
a linear or branched alkyl group, which reacting gives a maleated fatty acid. The method may optionally additionally consist essentially of or consist of reacting the maleated fatty acid with a multifunctional reactant selected from the group consisting of a polyol, an alkanolamine, an alkylene oxide and mixtures thereof to give a functionalized maleated fatty acid that has an acid number less than 10, where the reactants are as described in the claims.
Claims
1 . A method of improving the properties of a fluid selected from the group consisting of:
reducing the corrosivity of a fluid selected from the group consisting of a fuel, a lubricant, a motor oil, a transmission fluid, and an alcohol; and
improving the lubricating properties of a lubricant, a motor oil, a transmission fluid, and an alcohol;
the method comprising adding to the fluid an effective amount of a functionalized maleated fatty acid that is an ester, imide, and/or amide to either improve the lubricity and or reduce the corrosivity thereof.
2. The method claim 1 where the functionalized maleated fatty acid is made by a process comprising:
reacting an unsaturated fatty acid with an unsaturated compound selected from the group consisting of an unsaturated anhydride, a maleimide, and mixtures thereof where the unsaturated compound may be substituted with a linear or branched alkyl group, which reacting gives a maleated fatty acid;
reacting the maleated fatty acid with a multifunctional reactant selected from the group consisting of a polyol, an alkanolamine, an alkylene oxide and mixtures thereof to give a functionalized maleated fatty acid that has an acid number less than 10.
3. The method of claim 1 where the functionalized maleated fatty acid has a structure selected from the group consisting of:
where:
Ri is H or a hydrocarbyl group having 1 to 10 carbon atoms with zero, one or more double bonds, R2 is a direct bond or hydrocarbyl group having 1 to 10 carbons with one or more double bonds,
R3 is -(CH2CH20)n- or -(CH2CH(CH3)0)n- or combinations thereof, R4 is -(CH2CH20)nH, -(CH2CH(CH3)0)nH, -CH2CHOHCH2OH, or
-CH2CH2CH2CH2OH or combinations thereof, and
n is an integer from 1 to 1 0.
4. The method of claim 3 where the n is an integer from 1 to 5.
5. The method of claim 1 , 2 or 3 where the functionalized maleated fatty ester/imide/amide has an acid number less than 5.
6. The method of claim 1 , 2 or 3 where the effective amount of functionalized maleated fatty acid added to the fluid ranges from 1 to 3000 ppm.
7. The method of claim 2 where the unsaturated fatty acid has a weight average molecular weight between 300 to 5000.
8. The method of claim 2 or 7 where the unsaturated fatty acid is selected from the group consisting of monomeric, dimeric, trimeric crosslinked unsaturated fatty acids and mixtures thereof.
9. The method of claim 2 where the molar ratio of unsaturated fatty acid to unsaturated compound ranges from 1 :50 to 50:1 .
10. The method of claim 2 where the molar ratio of maleated fatty acid to multifunctional reactant ranges from 1 :20 to 20:1 .
1 1 . The method of claim 2 where:
the unsaturated fatty acid is selected from the group consisting of oleic acid, linoleic acid, a-linolenic acid, arachidonic acid, C10 to C40 unsaturated synthetic dimer fatty acids, dimer acid, unsaturated fatty acids having from 2 to 30 carbon atoms, , and mixtures thereof;
the polyol is selected from the group consisting of glycol, glycerol, alkyl phenols, alkyoxylated alkyl phenol, linear or branched alkyl alcohols, the polyol having from 2 to 30 carbon atoms and mixtures thereof;
the alkanolamine is selected from the group consisting of ethanolamine, propanolamine, diethanolamine, n-alkylethanolamine, isopropanol amine, diisopropanol amine, 3-amino-1 ,2-propanediol and mixtures thereof; and
the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
1 2. The method of claim 1 where the fluid is a fuel and the property that is improved is the fuel lubricity.
1 3. The method of claim 1 where the method is for reducing the corrosivity of a fuel, and the effective amount of functionalized maleated fatty ester/imide/amide ranges from 1 to 1 00 ppm.
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US12/873,475 US20120053101A1 (en) | 2010-09-01 | 2010-09-01 | Functionalized Maleated Fatty Acids as Non Acidic Fluid Additives |
PCT/US2011/047928 WO2012030524A2 (en) | 2010-09-01 | 2011-08-16 | Functionalized maleated fatty acids as non acidic fluid additives |
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CN103664841B (en) * | 2013-11-29 | 2015-07-08 | 山东艾孚特科技有限公司 | Preparation method of maleic anhydride grafted vegetable oil acid |
US9663726B2 (en) * | 2014-02-10 | 2017-05-30 | Baker Hughes Incorporated | Fluid compositions and methods for using cross-linked phenolic resins |
US11124692B2 (en) | 2017-12-08 | 2021-09-21 | Baker Hughes Holdings Llc | Methods of using ionic liquid based asphaltene inhibitors |
EA202091413A1 (en) | 2018-07-11 | 2020-09-24 | Бейкер Хьюз Холдингз Ллк | WELL ASPHALTEN INHIBITORS BASED ON IONIC LIQUID AND METHODS OF THEIR APPLICATION |
CN111349522B (en) * | 2018-12-21 | 2022-11-11 | 中国石油化工股份有限公司 | Preparation method and application of modified vegetable oil fatty acid methyl ester |
CN112779062B (en) * | 2019-11-11 | 2022-12-09 | 中国石油化工股份有限公司 | Low-sulfur diesel antiwear agent and preparation method and application thereof |
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US6239298B1 (en) * | 1998-05-26 | 2001-05-29 | International Lubricants Inc. | Fuel lubricity additives |
US7423000B2 (en) * | 1999-01-19 | 2008-09-09 | International Lubricants, Inc. | Non-phosphorous, non-metallic anti-wear compound and friction modifier |
MX2010000091A (en) * | 2007-07-03 | 2010-03-22 | Georgia Pacific Chemicals Llc | Chemical modification of maleated fatty acids. |
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