EP3536766A1 - Sels d'ammonium quaternaires fonctionnalisés par des agents de quaternisation époxyde - Google Patents

Sels d'ammonium quaternaires fonctionnalisés par des agents de quaternisation époxyde Download PDF

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Publication number
EP3536766A1
EP3536766A1 EP19166380.6A EP19166380A EP3536766A1 EP 3536766 A1 EP3536766 A1 EP 3536766A1 EP 19166380 A EP19166380 A EP 19166380A EP 3536766 A1 EP3536766 A1 EP 3536766A1
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Prior art keywords
composition
acid
hydrocarbyl
fuel
epoxide
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EP19166380.6A
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German (de)
English (en)
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EP3536766B1 (fr
EP3536766A8 (fr
Inventor
Paul E. Adams
James H. Bush
Hannah Greenfield
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Lubrizol Corp
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Lubrizol Corp
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    • 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
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
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    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
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    • C10L2270/00—Specifically adapted fuels
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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Definitions

  • the present technology is related to quaternary ammonium salts prepared with alcohol functionalized epoxide and/or C 4 to C 20 epoxide quaternizing agents, and the use of such quaternary ammonium salts in fuel and lubricant compositions to improve to improve the water shedding performance of the composition.
  • the invention further relates to a method of lubricating an internal combustion engine with the lubricant composition for at least one of antiwear, friction, detergency, dispersancy, and/or corrosion control performance.
  • demulsifiers In order to assist in the water shedding process, a class of molecules known as demulsifiers can be added to fuel or crude oil formulations, whether in the pipeline, at the pump or as an aftermarket additive. While demulsifiers can assist in the water shedding process, it would be desirable to provide a new detergent molecule that provides improved demulsification or water shedding performance.
  • quaternary ammoniums salts prepared with alcohol functionalized epoxides, C 4 to C 14 epoxides, and mixtures thereof result in quaternary ammonium salts that, when blended into diesel fuel, provide improved demulsification performance compared to quaternary ammonium salts prepared with other epoxides.
  • the present technology provides a composition comprising an epoxide quat prepared with alcohol functionalized epoxides, C 4 to C 14 epoxides, and mixtures thereof.
  • the epoxide quat itself can be the reaction product of (a) a quaternizable compound and (b) a quaternizing agent comprising alcohol functionalized epoxides, C 4 to C 14 epoxides, and mixtures thereof.
  • the quaternizable compound can be the reaction product of (i) a hydrocarbyl-substituted acylating agent, and (ii) a nitrogen containing compound having an oxygen or nitrogen atom capable of reacting with the hydrocarbyl-substituted acylating agent, and further having at least one quaternizable amino group.
  • the hydrocarbyl-substituent can have a number average molecular weight (M n ) of greater than 100, such as, for example, from 100 to 5000 as measured using gel permeation chromatography (GPC) based on a polystyrene calibration standard.
  • the quaternizable amino group can be a primary, secondary or tertiary amino group.
  • the hydrocarbyl-substituted acylating agent can be polyisobutenyl succinic anhydride or polyisobutenyl succinic acid.
  • the reaction to prepare the quaternizable compound of (a) can be carried out at a temperature of greater than 80 or 90 or 100 °C. In some embodiments, water of reaction can be removed. In some embodiments, the reaction to prepare the quaternizable compound of (a) can be carried out at a temperature of less than 80°C.
  • the epoxide quat is an imide containing quaternary ammonium salt. In an embodiment, the epoxide quat is an amide or ester containing quaternary ammonium salt.
  • the quaternizing agent can comprise, consist of, or consist essentially of alcohol functionalized epoxides. In still further embodiments, the quaternizing agent can comprise, consist of, or consist essentially of glycidol. In another embodiment, the quaternizing agent can comprise, consist of, or consist essentially of C 4 to C 14 epoxides. In another embodiment, the quaternizing agent can comprise, consist of, or consist essentially of 1,2-butylene oxide. In another embodiment, the quaternizing agent can comprise, consist of, or consist essentially of epoxyhexadecane.
  • the quaternizing agent can be employed in the presence of a protic solvent. In some embodiments, the quaternizing agent can be employed in the presence of 2-ethylhexanol, water, or mixtures thereof. In some embodiments, the quaternizing agent can be employed in the presence of an acid. In some embodiments, the quaternizing agent can be employed in the presence of an acid separate from the acid group present on the acylating agent. In some embodiments, the quaternizing agent can be employed in the presence of the acid group present in the structure of the acylating agent.
  • the compositions described above can further include at least one other additive.
  • the at least one other additive can be a detergent, a demulsifier, or a mixture thereof.
  • the at least one other additive can be at least one hydrocarbyl-substituted succinic acid.
  • the at least one other additive can be at least one hydrocarbyl-substituted quaternary ammonium salt.
  • the hydrocarbyl-substituent can be a polyisobutylene having a number average molecular weight (M n ) of from about 100 to about 5000.
  • the at least one other additive can be at least one Mannich compound.
  • a further aspect of the present technology includes a composition having an epoxide quat as described herein, and further having a fuel that is liquid at room temperature.
  • the fuel can be a diesel fuel.
  • a still further aspect of the present technology provides a method of operating an internal combustion engine.
  • the method can include the steps of (a) supplying to the engine a fuel composition and (b) operating said engine.
  • the fuel composition employed in the foregoing method can include (i) a fuel which is liquid at room temperature, and (ii) a composition comprising epoxide quat as described herein.
  • the method of operating an internal combustion engine can include the steps of (a) supplying a lubricating oil composition to the crankcase of the engine and (b) operating said engine.
  • the lubricating oil composition can include (i) oil of lubricating viscosity, and (ii) the epoxide quat as described herein.
  • Embodiments of the present technology may provide the use of the epoxide quat for at least one of antiwear performance, friction modification (particularly for enhancing fuel economy), detergent performance (particularly deposit control or varnish control), dispersancy (particularly soot control, or sludge control), or corrosion control.
  • a further embodiment of the present technology provides a method of improving water shedding, or demulsification, performance of a fuel composition.
  • the method includes employing in a fuel, which is liquid at room temperature, a composition containing an epoxide quat as described herein. Also provided is the use of a composition containing epoxide quat as described herein, to provide improved water shedding or demulsification performance in a fuel that is liquid at room temperature.
  • a composition comprising an epoxide quaternary ammonium salt (“epoxide quat”) is disclosed.
  • the epoxide quat may comprise the reaction product of a quaternizable compound and a quaternizing agent comprising alcohol functionalized epoxides, C 4 to C 14 epoxides, or mixtures thereof.
  • the quaternizing agent may be a C 4 to C 20 epoxide.
  • compositions comprising an epoxide quat may further comprising at least one other additive.
  • Suitable additive include, but are not limited to, detergents, dispersants, demulsifiers, lubricity agents, cold flow improvers, antioxidants, or mixtures thereof.
  • At least one hydrocarbyl group on the aromatic moiety is derived from polybutene.
  • the source of hydrocarbyl groups are above described polybutenes obtained by polymerization of isobutylene in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. Compounds and the processes for making these compounds are disclosed in U.S. Pat. Nos. 3,954,808 ; 5,336,278 ; 5,458,793 ; 5,620,949 ; 5,827,805 ; and 6,001,781 .
  • the amounts of the materials fed to the reaction mixture will normally approximate these ratios, although corrections may need to be made to compensate for greater or lesser reactivity of one component or antoher, in order to arrive at a reaction product with the desired ratio of monomers. Such corrections will be apparent to the person skilled in the art. While the three reactants can be condensed simultaneously to form the product, it is also possible to conduct the reaction sequentially, whereby the hydroxyaromatic is reacted first with either the carboxylic reactant and thereafter with the aldehyde or ketone, or vice versa. Compounds and the processes for making these compounds are disclosed in U.S. Pat. No. 5,620,949 .
  • composition of the present invention contains a nitrogen containing compound having an oxygen or nitrogen atom capable of reacting with the acylating agent and further having a quaternizable amino group.
  • a quaternizable amino group is any primary, secondary or tertiary amino group on the nitrogen containing compound that is available to react with a quaternizing agent to become a quaternary amino group.
  • the nitrogen containing compound can be represented by the following formulas: wherein X is an alkylene group containing 1 to 4 carbon atoms; R 2 may be a H or a hydrocarbyl group; and R 3 and R 4 are hydrocarbyl groups. wherein X is a alkylene group containing about 1 to about 4 carbon atoms; R3 and R4 are hydrocarbyl groups.
  • nitrogen containing compound capable of reacting with the acylating agent can include, but are not limited to, dimethylaminopropylamine, N,N-dimethyl-aminopropylamine, N,N-diethyl-aminopropylamine, N,N-dimethylaminoethylamine ethylenediamine, 1,2-propylenediamine, 1,3-propylene diamine, the isomeric butylenediamines, pentanediamines, hexanediamines, heptanediamines, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexaamine, hexamethylenetetramine, and bis(hexamethylene) triamine, the diaminobenzenes, the diaminopyridines or mixtures thereof.
  • the nitrogen containing compounds capable of reacting with the acylating agent and further having a quaternizable amino group can further include aminoalkyl substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine.
  • aminoalkyl substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine.
  • Additional nitrogen containing compounds capable of reacting with the acylating agent and having a quaternizable amino group include alkanolamines including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine, N-N-dimethylethanolamine, N-N-diethylethanolamine, 2-(diisopropylamino)ethanol, 2-(dibutylamino)ethanol, 3-dimethylamino-l-propanol, 3-diethylamino-1-propanol, 1-dimethylamino-2-propanol, 1-diethylamino-2-propanol, 2-dimethylamino-2-methyl-1-1propanol, 5-dimethylamino-2-prop
  • the nitrogen containing compound can be an imidazole, for example, as represented by the following formula: wherein R is an amine or alkanol capable of condensing with said hydrocarbyl-substituted acylating agent and having from 3 to 8 carbon atoms
  • the reaction between the hydrocarbyl substituted acylating agents and nitrogen containing compounds can be carried out at temperatures of greater than about 80 °C, or 90 °C, or in some cases 100 °C, such as between 100 and 150 or 200 °C, or 125 and 175 °C.
  • the reaction between the hydrocarbyl substituted acylating agents and the nitrogen containing compounds may be carried out at temperatures less than 80 °C, or 70 °C, or 60 °C, and in some cases between 40 °C and 80 °C.
  • water may be produced during the condensation, which is referred to herein as the water of reaction.
  • the water of reaction can be removed during the reaction, such that the water of reaction does not return to the reaction and further react.
  • the quaternary ammonium salt can be formed when the quaternizable compound, that is, the reaction products of the hydrocarbyl substituted acylating agent and nitrogen containing compounds described above, are reacted with a quaternizing agent.
  • Suitable quaternizing agents can include, for example, alcohol functionalized epoxides, C 4 to C 14 epoxides, and mixtures thereof. In yet another embodiment, the quaternizing agents may be C 4 to C 20 epoxides.
  • Epoxides suitable as quaternizing agents for the present technology include C 4 to C 14 epoxides.
  • Exemplary epoxides can be represented by the following formula: where R 1 , R 2 , R 3 and R 4 can be independently H, a C 4 to C 14 hydrocarbyl group, or an alcohol containing hydrocarbyl group.
  • the epoxides can be C 4 to C 14 epoxides.
  • the epoxides can be alcohol functionalized epoxides containing from 2 to 32, or from 3 to 28, or even from 3 to 24 carbon atoms.
  • the quaternizing agent can be employed in combination with an acid.
  • the acid used with the quaternizing agent may be a separate component, such as acetic acid, propionic acid, 2-ethylhexanoic acid, and the like.
  • a small amount of an acid component may be present, such as, about at ⁇ 0.2 or even ⁇ 0.1 moles of acid per mole of hydrocarbyl acylating agent.
  • the molar ratio of the condensation compound to quaternizing agent is 1:0.1 to 2, or 1:1 to 1.5, or 1:1 to 1.3.
  • R 24 can be a hydrocarbyl group containing from 92 to 215 carbon atoms, or from 107 to 200 or 210 carbon atoms, or from 120 to 195 carbon atoms, or from 135 to 190 or from 140 to 180 or 185 carbon atoms, or a hydrocarbyl group containing from 20 to 55 carbon atoms, or from 25 to 50, or from 28 to 43 or 47 carbon atoms.
  • the epoxide quats can comprise, consist essentially of, or consist of a cation represented by the following formulas: or wherein: R can be a C 1 to C 6 alkyl group; R 1 and R 2 , individually, can be a C 1 to C 6 hydrocarbyl group, for example a C 1 , C 2 , or C 3 alkyl group; R 3 , R 4 , R 5 and R 6 , individually, can be hydrogen or a C 1 to C 6 hydrocarbyl group, such as, for example, a C 1 , C 2 , or C 3 alkyl group; R 24 is a hydrocarbyl group containing from 5 to 400 carbon atoms, or from 15 or 25 to 300 or 350 carbon atoms, or from 50 or 120 to 250 carbon atoms, or from 135 to 200 carbon atoms; X 1 and X 2 , individually, can be H or a group derived from the quaternizing agent, so long as at least one of X 1 and
  • R 24 can be a hydrocarbyl group containing from 92 to 215 carbon atoms, or from 107 to 200 or 210 carbon atoms, or from 120 to 195 carbon atoms, or from 135 to 190 or from 140 to 180 or 185 carbon atoms, or a hydrocarbyl group containing from 20 to 55 carbon atoms, or from 25 to 50, or from 28 to 43 or 47 carbon atoms.
  • the epoxide quats can comprise, consist essentially of, or consist of a cation represented by the following formula: wherein: R 23 is a hydrocarbylene group containing from 1 to 20 carbon atoms; R 24 is a hydrocarbyl group containing from 5 to 400 carbon atoms, or from 15 or 25 to 300 or 350 carbon atoms, or from 50 or 120 to 250 carbon atoms, or from 135 to 200 carbon atoms; and X is a group derived from the quaternizing agent.
  • R 24 can be a hydrocarbyl group containing from 92 to 215 carbon atoms, or from 107 to 200 or 210 carbon atoms, or from 120 to 195 carbon atoms, or from 135 to 190 or from 140 to 180 or 185 carbon atoms, or a hydrocarbyl group containing from 20 to 55 carbon atoms, or from 25 to 50, or from 28 to 43 or 47 carbon atoms.
  • compositions of the present invention can comprise a fuel which is liquid at room temperature and is useful in fueling an engine.
  • the fuel is normally a liquid at ambient conditions e.g., room temperature (20 to 30 °C).
  • the fuel can be a hydrocarbon fuel, a nonhydrocarbon fuel, or a mixture thereof.
  • the hydrocarbon fuel can be a petroleum distillate to include a gasoline as defined by EN228 or ASTM specification D4814, or a diesel fuel as defined by EN590 or ASTM specification D975.
  • the fuel is a gasoline, and in other embodiments the fuel is a leaded gasoline, or a nonleaded gasoline.
  • the fuel is a diesel fuel.
  • the fuel contains 0 ppm to 1000 ppm, or 0 to 500 ppm, or 0 to 100 ppm, or 0 to 50 ppm, or 0 to 25 ppm, or 0 to 10 ppm, or 0 to 5 ppm of alkali metals, alkaline earth metals, transition metals or mixtures thereof.
  • the fuel contains 1 to 10 ppm by weight of alkali metals, alkaline earth metals, transition metals or mixtures thereof. It is well known in the art that a fuel containing alkali metals, alkaline earth metals, transition metals or mixtures thereof have a greater tendency to form deposits and therefore foul or plug common rail injectors.
  • the fuel of the invention is present in a fuel composition in a major amount that is generally greater than 50 percent by weight, and in other embodiments is present at greater than 90 percent by weight, greater than 95 percent by weight, greater than 99.5 percent by weight, or greater than 99.8 percent by weight.
  • Oils of lubricating viscosity may also be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • the five base oil groups are as follow; Group I: > 0.03% sulfur or ⁇ 90% saturates and viscosity index 80-120; Group II: ⁇ 0.03% sulfur and ⁇ 90% saturates and viscosity index 80-120; Group III: ⁇ 0.03% sulfur and ⁇ 90% saturates and viscosity index ⁇ 120; Group IV: all polyalphaolefins; Group V: all others.
  • Groups I, II and III are typically referred to as mineral oil base stocks.
  • Typical treat rates of the epoxide quats of the invention to lubricating oils is 0.1 to 10 wt % or 0.5 to 5 wt % or 0.5 to 2.5 wt % or 0.5 to 1 wt % or 0.1 to 0.5 wt % or 1 to 2 wt % based on a total weight of the lubricating oil.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt% the sum of the amount of the compound of the invention and the other performance additives.
  • the lubricating composition may be in the form of a concentrate and/or fully formulated lubricant. If the lubricating composition of the invention (comprising the additives disclosed herein) is in the form of a concentrate which may be combined with additional oil to from, in whole or in part, a finished lubricant), the ratio of the of these additive to the oil of lubricating viscosity and/or diluent oil include the ranged of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
  • the fuel and/or lubricant compositions of the present invention include the epoxide quats described above and may also include one or more additional additives. Such additional performance additives can be added to any of the compositions described depending on the results desired and the application in which the composition will be used.
  • any of the additional performance additives described herein can be used in any of the fuel and/or lubricant compositions of the invention, the following additional additives are particularly useful for fuel and/or lubricant compositions: antioxidants, corrosion inhibitors, detergent and/or dispersant additives other than those described above, cold flow improvers, foam inhibitors, demulsifiers, lubricity agents, metal deactivators, valve seat recession additives, biocides, antistatic agents, deicers, fluidizers, combustion improvers, seal swelling agents, wax control polymers, scale inhibitors, gas-hydrate inhibitors, or any combination thereof.
  • Demulsifiers suitable for use with the epoxide quats of the present technology can include, but not be limited to, arylsulfonates and polyalkoxylated alcohol, such as, for example, polyethylene and polypropylene oxide copolymers and the like.
  • the demulsifiers can also comprise nitrogen containing compounds such as oxazoline and imidazoline compounds and fatty amines, as well as Mannich compounds. Mannich compounds are the reaction products of alkylphenols and aldehydes (especially formaldehyde) and amines (especially amine condensates and polyalkylenepolyamines).
  • Mannich compounds are the reaction products of alkylphenols and aldehydes (especially formaldehyde) and amines (especially amine condensates and polyalkylenepolyamines).
  • demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol- and naphthalenesulfonates and the alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds such as alcohol alkoxylates, e.g.
  • demulsifiers Any of the commercially available demulsifiers may be employed, suitably in an amount sufficient to provide a treat level of from 5 to 50 ppm in the fuel. In an embodiment there is no demulsifier present in the fuel and/or lubricant composition.
  • the demulsifiers may be used alone or in combination. Some demulsifiers are commercially available, for example from Nalco or Baker Hughes.
  • Suitable antioxidants include for example hindered phenols or derivatives thereof and/or diarylamines or derivatives thereof.
  • Suitable detergent/dispersant additives include for example polyetheramines or nitrogen containing detergents, including but not limited to PIB amine detergents/dispersants, succinimide detergents/dispersants, and other quaternary salt detergents/dispersants including polyisobutylsuccinimide-derived quaternized PIB/amine and/or amide dispersants/detergents.
  • Suitable cold flow improvers include for example esterified copolymers of maleic anhydride and styrene and/or copolymers of ethylene and vinyl acetate.
  • Suitable lubricity improvers or friction modifiers are based typically on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described, for example, in WO 98/004656 , and glyceryl monooleate. The reaction products, described in U.S. Pat. No. 6,743,266 B2 , of natural or synthetic oils, for example triglycerides, and alkanolamines are also suitable as such lubricity improvers. Additional examples include commercial tall oil fatty acids containing polycyclic hydrocarbons and/or rosin acids. Suitable metal deactivators include for example aromatic triazoles or derivatives thereof, including but not limited to benzotriazole.
  • Suitable metal deactivators are, for example, salicylic acid derivatives such as N,N'-disalicylidene-1,2-propanediamine.
  • Suitable valve seat recession additives include for example alkali metal sulfosuccinate salts.
  • Suitable foam inhibitors and/or antifoams include for example organic silicones such as polydimethyl siloxane, polyethylsiloxane, polydiethylsiloxane, polyacrylates and polymethacrylates, trimethyl-triflouro-propylmethyl siloxane and the like.
  • Suitable fluidizers include for example mineral oils and/or poly(alpha-olefins) and/or polyethers.
  • the additional performance additives which may be present in the fuel and/or lubricant compositions of the invention, also include di-ester, di-amide, ester-amide, and ester-imide friction modifiers prepared by reacting an ⁇ -hydroxy acid with an amine and/or alcohol optionally in the presence of a known esterification catalyst.
  • ⁇ -hydroxy acids include glycolic acid, lactic acid, ⁇ -hydroxy dicarboxylic acid (such as tartaric acid) and/or an ⁇ -hydroxy tricarboxylic acid (such as citric acid), with an amine and/or alcohol, optionally in the presence of a known esterification catalyst.
  • friction modifiers often derived from tartaric acid, citric acid, or derivatives thereof, may be derived from amines and/or alcohols that are branched, resulting in friction modifiers that themselves have significant amounts of branched hydrocarbyl groups present within it structure.
  • suitable branched alcohols used to prepare such friction modifiers include 2-ethylhexanol, isotridecanol, Guerbet alcohols, and mixtures thereof.
  • Friction modifiers may be present at 0 to 6 wt % or 0.001 to 4 wt %, or 0.01 to 2 wt % or 0.05 to 3 wt % or 0.1 to 2 wt% or 0.1 to 1 wt % or 0.001 to 0.01 wt %.
  • the additional performance additives may comprise a detergent/dispersant comprising a hydrocarbyl substituted acylating agent.
  • the acylating agent may be, for example, a hydrocarbyl substituted succinic acid, or the condensation product of a hydrocarbyl substituted succinic acid with an amine or an alcohol; that is, a hydrocarbyl substituted succinimide or hydrocarbyl substituted succinate.
  • the detergent/dispersant may be a polyisobutenyl substituted succinic acid, amide or ester, wherein the polyisobutenyl substituent has a number average molecular weight of from about 100 to 5000.
  • the detergent may be a C 6 to C 18 substituted succinic acid, amide or ester.
  • hydrocarbyl substituted acylating agent detergents can be found from paragraph [0017] to [0036] of U.S. Publication 2011/0219674, published September 15, 2011 .
  • the additional detergent/dispersant is a quaternary ammoniums salt other than that of the present technology.
  • Additional quaternary ammoniums salts can be quaternary ammoniums salts prepared from hydrocarbyl substituted acylating agents, such as, for example, polyisobutyl succinic acids or anhydrides, having a hydrocarbyl substituent with a number average molecular weight of greater than 1200 M n , polyisobutyl succinic acids or anhydrides, having a hydrocarbyl substituent with a number average molecular weight of 300 to 750, or polyisobutyl succinic acids anhydrides, having a hydrocarbyl substituent with a number average molecular weight of 1000 M n .
  • hydrocarbyl substituted acylating agents such as, for example, polyisobutyl succinic acids or anhydrides, having a hydrocarbyl substituent with a number average molecular weight of greater than 1200 M n
  • the additional quaternary ammonium salts prepared from the reaction of nitrogen containing compound and a hydrocarbyl substituted acylating agent having a hydrocarbyl substituent with a number average molecular weight of 300 to 750 or 1300 to 3000 is an amide or ester.
  • the quaternary ammonium salts prepared from the reaction of nitrogen containing compound and a hydrocarbyl substituted acylating agent having a hydrocarbyl substituent with a number average molecular weight of greater than 1200 M n or having a hydrocarbyl substituent with a number average molecular weight of from 300 to 750 is an imide.
  • the hydrocarbyl substituted acylating agent can include a mono-, dimer or trimer carboxylic acid with 8 to 54 carbon atoms and is reactive with primary or secondary amines.
  • Suitable acids include, but are not limited to, the mono-, dimer, or trimer acids of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, ⁇ -linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.
  • the nitrogen containing compound of the additional quaternary ammonium salts is an imidazole or nitrogen containing compound of either of formulas.
  • R may be a C 1 to C 6 alkylene group; each of R 1 and R 2 , individually, may be a C 1 to C 6 hydrocarbylene group; and each of R 3 , R 4 , R 5 , and R 6 , individually, may be a hydrogen or a C 1 to C 6 hydrocarbyl group.
  • the quaternizing agent used to prepare the additional quaternary ammonium salts can be a dialkyl sulfate, an alkyl halide, a hydrocarbyl substituted carbonate, a hydrocarbyl epoxide, a carboxylate, alkyl esters, or mixtures thereof.
  • the quaternizing agent can be a hydrocarbyl epoxide.
  • the quaternizing agent can be a hydrocarbyl epoxide in combination with an acid.
  • the quaternizing agent can be a salicylate, oxalate or terephthalate.
  • the hydrocarbyl epoxide is an alcohol functionalized epoxides or C 4 to C 14 epoxides.
  • the quaternizing agent is multi-functional resulting in the additional quaternary ammonium salts being coupled quaternary ammoniums salts.
  • Additional quaternary ammonium salts include, but are not limited to quaternary ammonium salts having a hydrophobic moiety in the anion.
  • Exemplary compounds include quaternary ammonium compounds having the formula below: wherein R 0 , R 1 , R 2 and R 3 is each individually an optionally substituted alkyl, alkenyl or aryl group and R includes an optionally substituted hydrocarbyl moiety having at least 5 carbon atoms.
  • Additional quaternary ammonium salts may also include polyetheramines that are the reaction products of a polyether-substituted amine comprising at least one tertiary quaternizable amino group and a quaternizing agent that converts the tertiary amino group to a quaternary ammonium group.
  • Dispersants can also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in U.S. Patent 4,654,403 .
  • the fuel and/or lubricant compositions of the invention may include a detergent additive, different from the disclosed epoxide quat technology.
  • a detergent additive different from the disclosed epoxide quat technology.
  • Most conventional detergents used in the field of engine lubrication obtain most or all of their basicity or TBN from the presence of basic metal-containing compounds (metal hydroxides, oxides, or carbonates, typically based on such metals as calcium, magnesium, or sodium).
  • Such metallic overbased detergents also referred to as overbased or superbased salts, are generally single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the overbased materials are typically prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid such as carbon dioxide) with a mixture of an acidic organic compound (also referred to as a substrate), a stoichiometric excess of a metal base, typically in a reaction medium of an one inert, organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for the acidic organic substrate. Typically also a small amount of promoter such as a phenol or alcohol is present, and in some cases a small amount of water.
  • the acidic organic substrate will normally have a sufficient number of carbon atoms to provide a degree of solubility in oil.
  • Patents describing techniques for making basic metallic salts of sulfonic acids, carboxylic acids, phenols, phosphonic acids, and mixtures of any two or more of these include U.S. Patents 2,501,731 ; 2,616,905 ; 2,616,911 ; 2,616,925 ; 2,777,874 ; 3,256,186 ; 3,384,585 ; 3,365,396 ; 3,320,162 ; 3,318,809 ; 3,488,284 ; and 3,629,109 .
  • Salixarate detergents are described in U.S. patent 6,200,936 .
  • the detergent may contain a metal-containing salicylate detergent, such as an overbased calcium hydrocarbyl-substituted salicylate detergent and are described in U.S. Patents 5,688,751 and 4,627,928 .
  • Viscosity improvers may be included in the fuel and/or lubricant compositions of this invention.
  • Viscosity improvers are usually polymers, including polyisobutenes, polymethacrylates (PMA) and polymethacrylic acid esters, hydrogenated diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, hydrogenated alkenylarene-conjugated diene copolymers and polyolefins.
  • PMA's are prepared from mixtures of methacrylate monomers having different alkyl groups. The alkyl groups may be either straight chain or branched chain groups containing from 1 to 18 carbon atoms. Most PMA's are viscosity modifiers as well as pour point depressants.
  • Multifunctional viscosity improvers which also have dispersant and/or antioxidancy properties are known and may optionally be used in the fuel and/or lubricant compositions.
  • Dispersant viscosity modifiers are one example of such multifunctional additives.
  • DVM are typically prepared by copolymerizing a small amount of a nitrogen-containing monomer with alkyl methacrylates, resulting in an additive with some combination of dispersancy, viscosity modification, pour point depressancy and dispersancy.
  • Vinyl pyridine, N-vinyl pyrrolidone and N,N'-dimethylaminoethyl methacrylate are examples of nitrogen-containing monomers.
  • Polyacrylates obtained from the polymerization or copolymerization of one or more alkyl acrylates also are useful as viscosity modifiers.
  • Anti-wear agents may be used in the fuel and/or lubricant compositions provide herein.
  • Anti-wear agents can in some embodiments include phosphorus-containing antiwear/extreme pressure agents such as metal thiophosphates, phosphoric acid esters and salts thereof, phosphorus-containing carboxylic acids, esters, ethers, and amides; and phosphites.
  • a phosphorus antiwear agent may be present in an amount to deliver 0.01 to 0.2 or 0.015 to 0.15 or 0.02 to 0.1 or 0.025 to 0.08 percent by weight phosphorus.
  • the antiwear agent is a zinc dialkyldithiophosphate (ZDP).
  • Non-phosphorus-containing anti-wear agents include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.
  • the fuel and/or lubricant compositions of the invention are free of phosphorus-containing antiwear/extreme pressure agents.
  • Foam inhibitors that may be useful in fuel and/or lubricant compositions of the invention include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
  • the disclosed technology may also be used with a silicone-containing antifoam agent in combination with a C 5 - C 17 alcohol.
  • Pour point depressants that may be useful in fuel and/or lubricant compositions of the invention include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates or polyacrylamides.
  • Metal deactivators may be chosen from a derivative of benzotriazole (typically tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole, 1-amino-2-propanol, a derivative of dimercaptothiadiazole, octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride and/or a fatty acid such as oleic acid with a polyamine.
  • the metal deactivators may also be described as corrosion inhibitors.
  • demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol- and naphthalenesulfonates and the alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g.
  • tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example including in the form of EO/PO block copolymers, polyethyleneimines or else polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Any of the commercially available demulsifiers may be employed, suitably in an amount sufficient to provide a treat level of from 5 to 50 ppm in the fuel.
  • the fuel composition of the invention does not comprise a demulsifier.
  • the demulsifiers may be used alone or in combination. Some demulsifiers are commercially available, for example from Nalco or Baker Hughes.
  • Typical treat rates of the demulsifiers to a fuel may range from 0 to 50 ppm by total weight of the fuel, or 5 to 50 ppm, or 5 to 25 ppm, or 5 to 20 ppm.
  • the disclosed technology may also be used with demulsifiers comprising a hydrocarbyl-substituted dicarboxylic acid in the form of the free acid, or in the form of the anhydride which may be an intramolecular anhydride, such as succinic, glutaric, or phthalic anhydride, or an intermolecular anhydride linking two dicarboxylic acid molecules together.
  • the hydrocarbyl substituent may have from 12 to 2000 carbon atoms and may include polyisobutenyl substituents having a number average molecular weight of 300 to 2800.
  • hydrocarbyl-substituted dicarboxylic acids include, but are not limited to, hydrocarbyl-substituted acids derived from malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, undecanedioic, dodecanedioic, phthalic, isophthalic, terphthalic, o-, m-, or p-phenylene diacetic, maleic, fumaric, or glutaconic acids.
  • a fuel composition comprises the epoxide quats of the present invention and an additional detergent/dispersant.
  • Customary detergent/dispersant additives are preferably amphiphilic substances which possess at least one hydrophobic hydrocarbon radical with a number-average molecular weight of 100 to 10000 and at least one polar moiety selected from (i) Mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties; (ii) Hydroxyl groups in combination with mono or polyamino groups, at least one nitrogen atoms having basic properties; (iii) Carboxyl groups or their alkali metal or alkaline earth metal salts; (iv) Sulfonic acid groups or their alkali metal or alkaline earth metal salts; (v) Polyoxy-C 2 to C 4 alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups; (vi) Carboxylic ester groups
  • the hydrophobic hydrocarbon radical in the above detergent/dispersant additives which ensures the adequate solubility in the fuel, has a number-average molecular weight (M n ) of 85 to 20,000, of 100 to 10,000, or 300 to 5000
  • the detergent/dispersant additives have a M n of 300 to 3000, of 500 to 2500, of 700 to 2500, or 800 to 1500.
  • Typical hydrophobic hydrocarbon radicals may be polypropenyl, polybutenyl and polyisobutenyl radicals, with a number average molecular weight M n , of 300 to 5000, of 300 to 3000, of 500 to 2500, or 700 to 2500.
  • the detergent/dispersant additives have a M n of 800 to 1500.
  • the additional performance additives may comprise a high TBN nitrogen containing detergent/dispersant, such as a succinimide, that is the condensation product of a hydrocarbyl-substituted succinic anhydride with a poly(alkyleneamine).
  • a high TBN nitrogen containing detergent/dispersant such as a succinimide
  • succinimide that is the condensation product of a hydrocarbyl-substituted succinic anhydride with a poly(alkyleneamine).
  • Succinimide detergents/dispersants are more fully described in U.S. patents 4,234,435 and 3,172,892 .
  • Another class of ashless dispersant is high molecular weight esters, prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol. Such materials are described in more detail in U.S. Patent 3,381,022
  • Nitrogen-containing detergents are the reaction products of a carboxylic acid-derived acylating agent and an amine.
  • the acylating agent can vary from formic acid and its acylating derivatives to acylating agents having high molecular weight aliphatic substituents of up to 5,000, 10,000 or 20,000 carbon atoms.
  • the amino compounds can vary from ammonia itself to amines typically having aliphatic substituents of up to about 30 carbon atoms, and up to 11 nitrogen atoms.
  • Acylated amino compounds suitable for use in the present invention are those formed by the reaction of an acylating agent having a hydrocarbyl substituent of at least 8 carbon atoms and a compound comprising at least one primary or secondary amine group.
  • the acylating agent may be a mono- or polycarboxylic acid (or reactive equivalent thereof) for example a substituted succinic, phthalic or propionic acid and the amino compound may be a polyamine or a mixture of polyamines, for example a mixture of ethylene polyamines. Alternatively the amine may be a hydroxyalkyl-substituted polyamine.
  • the hydrocarbyl substituent in such acylating agents may comprise at least 10 carbon atoms. In one embodiment, the hydrocarbyl substituent may comprise at least 12, for example 30 or 50 carbon atoms. In yet another embodiment, it may comprise up to 200 carbon atoms.
  • the hydrocarbyl substituent of the acylating agent may have a number average molecular weight (M n ) of 170 to 2800, for example from 250 to 1500.
  • the substituent's M n may range from 500 to 1500, or alternatively from500 to 1100.
  • the substituent's M n may range from 700 to 1300.
  • the hydrocarbyl substituent may have a number average molecular weight of 700 to 1000, or 700 to 850, or, for example, 750.
  • Mannich bases Another class of ashless dispersant is Mannich bases. These are materials which are formed by the condensation of a higher molecular weight, alkyl substituted phenol, an alkylene polyamine, and an aldehyde such as formaldehyde and are described in more detail in U.S. Patent 3,634,515 .
  • a useful nitrogen containing dispersant includes the product of a Mannich reaction between (a) an aldehyde, (b) a polyamine, and (c) an optionally substituted phenol.
  • the phenol may be substituted such that the Mannich product has a molecular weight of less than 7500.
  • the molecular weight may be less than 2000, less than 1500, less than 1300, or for example, less than 1200, less than 1100, less than 1000.
  • the Mannich product has a molecular weight of less than 900, less than 850, or less than 800, less than 500, or less than 400.
  • the substituted phenol may be substituted with up to 4 groups on the aromatic ring.
  • the phenol may be a tri or di-substituted phenol.
  • the phenol may be a mono-substituted phenol.
  • the substitution may be at the ortho, and/or meta, and/or para position(s).
  • the molar ratio of the aldehyde to amine is from 4:1 to 1:1 or, from 2:1 to 1:1.
  • the molar ratio of the aldehyde to phenol may be at least 0.75:1; or 0.75 to 1 to 4:1, or 1:1 to 4:1, or 1:1 to 2:1.
  • the molar ratio of the phenol to amine can be at least 1.5:1, at least 1.6:1, at least 1.7:1, for example at least 1.8:1, or at least 1.9:1.
  • the molar ratio of phenol to amine may be up to 5:1; for example it may be up to 4:1, or up to 3.5:1. Suitably it is up to 3.25:1, up to 3:1, up to 2.5:1, up to 2.3:1 or up to 2.1:1.
  • polymeric dispersant additives which are generally hydrocarbon-based polymers which contain polar functionality to impart dispersancy characteristics to the polymer.
  • An amine is typically employed in preparing the high TBN nitrogen-containing dispersant.
  • One or more poly(alkyleneamine)s may be used, and these may comprise one or more poly(ethyleneamine)s having 3 to 5 ethylene units and 4 to 6 nitrogen units.
  • Such materials include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA).
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • PEHA pentaethylenehexamine
  • Such materials are typically commercially available as mixtures of various isomers containing a range number of ethylene units and nitrogen atoms, as well as a variety of isomeric structures, including various cyclic structures.
  • the poly(alkyleneamine) may likewise comprise relatively higher molecular weight amines known in the industry as ethylene
  • the fuel composition can additionally comprise quaternary ammonium salts other than the epoxide quats disclosed herein.
  • the other quaternary ammonium salts can comprise (a) a compound comprising (i) at least one tertiary amino group as described above, and (ii) a hydrocarbyl-substituent having a number average molecular weight of 100 to 5000, or 250 to 4000, or 100 to 4000, or 100 to 2500, or 3000; and (b) a quaternizing agent suitable for converting the tertiary amino group of (a)(i) to a quaternary nitrogen, as described above.
  • the other quaternary ammonium salts are more thoroughly described in U.S.
  • the additional quaternary ammoniums salts other than the disclosed technology can be quaternary ammoniums salts prepared from hydrocarbyl substituted acylating agents, such as, for example, polyisobutyl succinic acids or anhydrides, having a hydrocarbyl substituent with a number average molecular weight of greater than 1200 M n , polyisobutyl succinic acids or anhydrides, having a hydrocarbyl substituent with a number average molecular weight of 300 to 750, or polyisobutyl succinic acids or anhydrides, having a hydrocarbyl substituent with a number average molecular weight of 1000 M n .
  • hydrocarbyl substituted acylating agents such as, for example, polyisobutyl succinic acids or anhydrides, having a hydrocarbyl substituent with a number average molecular weight of greater than 1200 M n , polyisobutyl succinic acids or anhydrides, having a hydrocar
  • the fuel composition comprising the epoxide quats disclosed herein can further comprise additional quaternary ammonium salts that are amides or esters.
  • the additional amide or ester quats are prepared from the reaction of a nitrogen containing compound and a hydrocarbyl substituted acylating agent having a hydrocarbyl substituent with a number average molecular weight of 300 to 750, or 1300 to 3000.
  • the fuel compositions can further can further comprise additional quaternary ammonium salts that are imides.
  • the imide quats are prepared from the reaction of nitrogen containing compound and a hydrocarbyl substituted acylating agent having a hydrocarbyl substituent with a number average molecular weight of greater than 1200 M n or, having a hydrocarbyl substituent with a number average molecular weight of 300 to 750.
  • the hydrocarbyl substituted acylating agent may also be a copolymer formed by copolymerizing at least one monomer that is an ethylenically unsaturated hydrocarbon having 2 to 100 carbon atoms.
  • the monomer may be linear, branched, or cyclic.
  • the monomer may have oxygen or nitrogen substituents, but will not react with amines or alcohols.
  • the monomer may be reacted with a second monomer that is a carboxylic acid or carboxylic acid derivative having 3 to 12 carbon atoms.
  • the second monomer may have one or two carboxylic acid functional groups and is reactive with amines or alcohols.
  • the hydrocarbyl substituted acylating agent copolymer has a number average molecular weight Mn of 500 to 20,000.
  • the hydrocarbyl substituted acylating agent may be a terpolymer that is the reaction product of ethylene and at least one monomer that is an ethylenically unsaturated monomer having at least one tertiary nitrogen atom, with (i) an alkenyl ester of one or more aliphatic monocarboxylic acids having 1 to 24 carbon atoms or (ii) an alkyl ester of acrylic or methacrylic acid.
  • the nitrogen containing compound of the additional quaternary ammonium salts is an imidazole or nitrogen containing compound of either of formulas.
  • R may be a C 1 to C 6 alkylene group; each of R 1 and R 2 , individually, may be a C 1 to C 6 hydrocarbylene group; and each of R 3 , R 4 , R 5 , and R 6 , individually, may be a hydrogen or a C 1 to C 6 hydrocarbyl group.
  • R 1 or R 2 can be, for example, a C 1 , C 2 or C 3 alkylene group.
  • each R 3 , R 4 , R 5 , R 6 can be, for example, H or a C 1 , C 2 or C 3 alkyl group.
  • the quaternizing agent used to prepare the additional quaternary ammonium salts can be a dialkyl sulfate, an alkyl halide, a hydrocarbyl substituted carbonate, a hydrocarbyl epoxide, a carboxylate, alkyl esters, or mixtures thereof.
  • the quaternizing agent can be a hydrocarbyl epoxide.
  • the quaternizing agent can be a hydrocarbyl epoxide in combination with an acid.
  • the quaternizing agent can be a salicylate, oxalate or terephthalate.
  • the hydrocarbyl epoxide is an alcohol functionalized epoxides or C 4 to C 14 epoxides.
  • the quaternizing agent is multi-functional resulting in the additional quaternary ammonium salts being a coupled quaternary ammoniums salts.
  • Typical treat rates of additional detergents/dispersants to a fuel of the invention is 0 to 500 ppm, or 0 to 250 ppm, or 0 to 100 ppm, or 5 to 250 ppm, or 5 to 100 ppm, or 10 to 100 ppm.
  • a fuel composition comprises the quaternary ammonium salts of the present invention and a cold flow improver.
  • the cold flow improver is typically selected from (1) copolymers of a C 2 - to C 40 -olefin with at least one further ethylenically unsaturated monomer; (2) comb polymers; (3) polyoxyalkylenes; (4) polar nitrogen compounds; (5) sulfocarboxylic acids or sulfonic acids or derivatives thereof; and (6) poly(meth)acrylic esters. It is possible to use either mixtures of different representatives from one of the particular classes (1) to (6) or mixtures of representatives from different classes (1) to (6).
  • Suitable C 2 - to C 40 -olefin monomers for the copolymers of class (1) are, for example, those having 2 to 20 and especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2 carbon-carbon double bonds, especially having one carbon-carbon double bond.
  • the carbon-carbon double bond may be arranged either terminally (a-olefins) or internally.
  • the at least one further ethylenically unsaturated monomer of class (1) is preferably selected from alkenyl carboxylates; for example, C 2 - to C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched among these, preference is given to the vinyl esters, examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, (meth)acrylic esters; for example, esters of (meth)acrylic acid with C 1 - to C 20 -alkanols, especially C 1 - to C 10 -alkanols, in particular with methanol, ethanol, propano
  • Suitable copolymers of class (1) are also those which comprise two or more different alkenyl carboxylates in copolymerized form, which differ in the alkenyl function and/or in the carboxylic acid group.
  • copolymers which, as well as the alkenyl carboxylate(s), comprise at least one olefin and/or at least one (meth)acrylic ester in copolymerized form.
  • Terpolymers of a C 2 - to C 40 - ⁇ -olefin, a C 1 - to C 20 -alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 - to C 14 -alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also suitable as copolymers of class (K1).
  • Terpolymers of this kind are described in WO 2005/054314 .
  • a typical terpolymer of this kind is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.
  • the at least one or the further ethylenically unsaturated monomer(s) are copolymerized in the copolymers of class (1) in an amount of preferably 1 to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight, based on the overall copolymer.
  • the main proportion in terms of weight of the monomer units in the copolymers of class (1) therefore originates generally from the C 2 to C 40 base olefins.
  • the copolymers of class (1) can have a number-average molecular weight M n of 1000 to 20,000, or 1000 to 10,000, or 1000 to 8000.
  • Typical comb polymers of component (2) are, for example, obtainable by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms.
  • Further suitable comb polymers are copolymers of a-olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
  • Suitable comb polymers may also be polyfumarates or polymaleates. Homo- and copolymers of vinyl ethers are also suitable comb polymers.
  • Comb polymers suitable as components of class (2) are, for example, also those described in WO 2004/035715 and in " Comb-Like Polymers. Structure and Properties", N. A. Platé and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974 ). Mixtures of comb polymers are also suitable.
  • Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs.
  • Secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures in particular amine mixtures obtainable on the industrial scale, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, "Amines, aliphatic" chapter .
  • metal ratio is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
  • a neutral metal salt has a metal ratio of one.
  • a salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5.
  • metal ratio is also explained in standard textbook entitled “ Chemistry and Technology of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, page 219, sub-heading 7.25 .
  • the overbased metal-containing detergent may be chosen from non-sulfur-containing phenates, sulfur-containing phenates, sulfonates, salixarates, salicylates, carboxylates, and mixtures thereof, or borated equivalents thereof.
  • the overbased detergent may be borated with a borating agent such as boric acid.
  • the overbased detergent may be non-sulfur containing phenates, sulfur containing phenates, sulfonates, or mixtures therof.
  • An engine oil lubricant may further comprise an overbased sulfonate detergent present at 0.01 wt % to 0.9 wt %, or 0.05 wt % to 0.8 wt %, or 0.1 wt % to 0.7 wt %, or 0.2 wt % to 0.6 wt %.
  • the overbased sulfonate detergent may have a metal ratio of 12 to less than 20, or 12 to 18, or 20 to 30, or 22 to 25.
  • An engine oil lubricant composition may also include one or more detergents in addition to the overbased sulfonate.
  • Overbased sulfonates typically have a total base number of 250 to 600, or 300 to 500 (on an oil free basis).
  • Overbased detergents are known in the art.
  • the sulfonate detergent may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted as US 7,407,919 ).
  • Linear alkyl benzenes may have the benzene ring attached anywhere on the linear chain, usually at the 2, 3, or 4 position, or mixtures thereof.
  • the predominantly linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy.
  • the overbased sulfonate detergent comprises an overbased calcium sulfonate.
  • the calcium sulfonate detergent may have a metal ratio of 18 to 40 and a TBN of 300 to 500, or 325 to 425.
  • the other detergents may have a metal of the metal-containing detergent may also include "hybrid" detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described; for example, in US Patents 6,429,178 ; 6,429,179 ; 6,153,565 ; and 6,281,179 .
  • phenate/salicylates e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described; for example, in US Patents 6,429,178 ; 6,429,179 ; 6,153,565 ; and 6,281,179 .
  • the lubricating composition comprises less than 0.2 wt %, or less than 0.1 wt %, or even less than 0.05 wt % of a phenate detergent derived from PDDP. In one embodiment, the lubricant composition comprises a phenate detergent that is not derived from PDDP.
  • the succinimide dispersant may be derived from an aliphatic polyamine, or mixtures thereof.
  • the aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof.
  • the aliphatic polyamine may be ethylenepolyamine.
  • the aliphatic polyamine may be chosen from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
  • the dispersant may be borated or non-borated.
  • a borated dispersant may be a succinimide dispersant.
  • the ashless dispersant may be boron-containing, i.e., has incorporated boron and delivers said boron to the lubricant composition.
  • the boron-containing dispersant may be present in an amount to deliver at least 25 ppm boron, at least 50 ppm boron, or at least 100 ppm boron to the lubricant composition.
  • the lubricant composition may be free of a boron-containing dispersant, i.e. delivers no more than 10 ppm boron to the final formulation.
  • the dispersant may also be obtained/obtainable from a chlorine-assisted process, often involving Diels-Alder chemistry, leading to formation of carbocyclic linkages.
  • the process is known to a person skilled in the art.
  • the chlorine-assisted process may produce a dispersant that is a polyisobutylene succinimide having a carbocyclic ring present on 50 mole % or more, or 60 to 100 mole % of the dispersant molecules. Both the thermal and chlorine-assisted processes are described in greater detail in U.S. Patent 7,615,521 , columns 4-5 and preparative examples A and B.
  • the dispersant may have a carbonyl to nitrogen ratio (CO:N ratio) of 5:1 to 1:10, 2:1 to 1:10, or 2:1 to 1:5, or 2:1 to 1:2.
  • the dispersant may have a CO:N ratio of 2:1 to 1:10, or 2:1 to 1:5, or 2:1 to 1:2, or 1:1.4 to 1:0.6.
  • the dispersant may be present at 0 wt % to 20 wt %, 0.1 wt % to 15 wt %, or 0.5 wt % to 9 wt %, or 1 wt % to 8.5 wt % or 1.5 to 5 wt % of the lubricant composition.
  • the diarylamine or alkylated diarylamine may be a phenyl- ⁇ -naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or mixtures thereof.
  • the alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof.
  • the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof.
  • the alkylated diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine.
  • the alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.
  • hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
  • the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105 .
  • molybdenum dithiocarbamates which may be used as an antioxidant, include commercial materials sold under the trade names such as Molyvan 822®, Molyvan® A and Molyvan® 855 from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-LubeTM S-100, S-165, S-600 and 525, or mixtures thereof.
  • an engine oil lubricant composition comprising the epoxide quats of the present technology further includes a viscosity modifier.
  • the viscosity modifier is known in the art and may include hydrogenated styrene-butadiene rubbers, ethylene-propylene copolymers, ethylene copolymers with propylene and higher olefins, polymethacrylates, polyacrylates, hydrogenated styrene-isoprene polymers, hydrogenated diene polymers, polyalkyl styrenes, polyolefins, esters of maleic anhydride-olefin copolymers (such as those described in International Application WO 2010/014655 ), esters of maleic anhydride-styrene copolymers, or mixtures thereof.
  • the viscosity modifier may be a dispersant viscosity modifier.
  • the dispersant viscosity modifier may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine.
  • the dispersant viscosity modifier may be prepared by grafting of an olefinic carboxylic acid acylating agent onto a polymer of 15 to 80 mole percent of ethylene, from 20 to 85 mole percent of C 3-10 ⁇ -monoolefin, and from 0 to 15 mole percent of non-conjugated diene or triene, said polymer having an average molecular weight ranging from 5000 to 20,000, and further reacting said grafted polymer with an amine (typically an aromatic amine).
  • an amine typically an aromatic amine
  • the dispersant viscosity modifier may include those described in U.S. Patent 4,863,623 (see column 2, line 15 to column 3, line 52) or in International Publication WO2006/015130 (see page 2, paragraph [0008] and preparative examples are described paragraphs [0065] to [0073]).
  • the dispersant viscosity modifier may include those described in U.S. Patent US 7,790,661 column 2, line 48 to column 10, line 38.
  • an engine oil lubricant composition comprising the epoxide quats of the present technology further includes a friction modifier.
  • the friction modifier may be chosen from long chain fatty acid derivatives of amines, long chain fatty esters, or derivatives of long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty malic esters and imides, fatty (poly)glycolates; and fatty glycolamides.
  • the friction modifier may be present at 0 wt % to 6 wt %, or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % of the lubricant composition.
  • fatty alkyl or "fatty" in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.
  • Suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters such as glycerol mono-oleate; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines;
  • Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.
  • the friction modifier may be a long chain fatty acid ester.
  • the long chain fatty acid ester may be a mono-ester and in another embodiment the long chain fatty acid ester may be a triglyceride.
  • An engine oil lubricant composition comprising the epoxide quats of the present technology optionally further includes at least one antiwear agent.
  • suitable antiwear agents include titanium compounds, tartaric acid derivatives such as tartrate esters, amides or tartrimides, malic acid derivatives, citric acid derivatives, glycolic acid derivatives, oil soluble amine salts of phosphorus compounds different from that of the invention, sulfurized olefins, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulphides.
  • the antiwear agent may in one embodiment include a tartrate or tartrimide as disclosed in International Publication WO 2006/044411 or Canadian Patent CA 1 183 125 .
  • the tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups is at least 8.
  • the antiwear agent may in one embodiment include a citrate as is disclosed in US Patent Application 20050198894 .
  • oil-soluble titanium compounds as disclosed in US 7,727,943 and US2006/0014651 .
  • the oil-soluble titanium compounds may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions.
  • the oil soluble titanium compound is a titanium (IV) alkoxide.
  • the titanium alkoxide is formed from a monohydric alcohol, a polyol or mixtures thereof.
  • the monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms.
  • the titanium alkoxide is titanium (IV) isopropoxide.
  • the titanium alkoxide is titanium (IV) 2-ethylhexoxide.
  • the titanium compound comprises the alkoxide of a vicinal 1,2-diol or polyol.
  • the 1,2-vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty acid is oleic acid.
  • the oil soluble titanium compound is a titanium carboxylate.
  • the titanium (IV) carboxylate is titanium neodecanoate.
  • An engine oil lubricant composition comprising the epoxide quats of the present technology may further include a phosphorus-containing antiwear agent different from that of the invention.
  • the phosphorus-containing antiwear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium phosphate salts, or mixtures thereof.
  • an engine oil lubricant composition may further comprise a phosphorus-containing antiwear agent, typically zinc dialkyldithiophosphate.
  • Zinc dialkyldithiophosphates are known in the art.
  • Examples of zinc dithiophosphates include zinc isopropyl methylamyl dithiophosphate, zinc isopropyl isooctyl dithiophosphate, zinc di(cyclohexyl) dithiophosphate, zinc isobutyl 2-ethylhexyl dithiophosphate, zinc isopropyl 2-ethylhexyl dithiophosphate, zinc isobutyl isoamyl dithiophosphate, zinc isopropyl n-butyl dithiophosphate, and combinations thereof.
  • Zinc dialkyldithiophosphate may be present in amount to provide 0.01 wt % to 0.1 wt % phosphorus to the lubricating composition, or to provide 0.015 wt % to 0.075 wt % phosphorus, or 0.02 wt % to 0.05 wt % phosphorus to the lubricating composition.
  • the antiwear agent may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricant composition.
  • an engine oil lubricant composition comprising the epoxide quats of the present technology further comprises 0.01 to 5 wt % or 0.1 to 2 wt % of an ashless antiwear agent that may be a compound obtained/obtainable by a process comprising reacting a glycolic acid, a 2-halo-acetic acid, or a lactic acid, or an alkali or alkaline metal salt thereof, (typically glycolic acid or a 2-halo-acetic acid) with at least one member selected from the group consisting of an amine, an alcohol, and an aminoalcohol.
  • an ashless antiwear agent may be a compound obtained/obtainable by a process comprising reacting a glycolic acid, a 2-halo-acetic acid, or a lactic acid, or an alkali or alkaline metal salt thereof, (typically glycolic acid or a 2-halo-acetic acid) with at least one member selected from the group consisting of an amine, an alcohol, and an aminoalcohol.
  • the invention is useful in a liquid fuel or an oil of lubricating viscosity in an internal combustion engine.
  • the internal combustion engine may be a gasoline or diesel engine.
  • Exemplary internal combustion engines include, but are not limited to, spark ignition and compression ignition engines; 2-stroke or 4-stroke cycles; liquid fuel supplied via direct injection, indirect injection, port injection and carburetor; common rail and unit injector systems; light (e.g. passenger car) and heavy duty (e.g. commercial truck) engines; and engines fuelled with hydrocarbon and non-hydrocarbon fuels and mixtures thereof.
  • the engines may be part of integrated emissions systems incorporating such elements as; EGR systems; aftertreatment including three-way catalyst, oxidation catalyst, NO x absorbers and catalysts, catalyzed and non-catalyzed particulate traps optionally employing fuel-borne catalyst; variable valve timing; and injection timing and rate shaping.
  • the technology may be used with diesel engines having direct fuel injection systems wherein the fuel is injected directly into the engine's combustion chamber.
  • the ignition pressures may be greater than 1000 bar and, in one embodiment, the ignition pressure may be greater than 1350 bar.
  • the direct fuel injection system maybe a high-pressure direct fuel injection system having ignition pressures greater than 1350 bar.
  • Exemplary types of high-pressure direct fuel injection systems include, but are not limited to, unit direct injection (or "pump and nozzle") systems, and common rail systems.
  • unit direct injection systems the high-pressure fuel pump, fuel metering system and fuel injector are combined into one apparatus.
  • Common rail systems have a series of injectors connected to the same pressure accumulator, or rail. The rail in turn, is connected to a high-pressure fuel pump.
  • the unit direct injection or common rail systems may further comprise an optional turbocharged or supercharged direct injection system.
  • IDIDs may be more problematic than in traditional diesel engines.
  • IDIDs can form on injector moving parts, such as the needle and command piston or control valve. IDIDs can hinder the movement of the injector parts, impairing the injection timing and the quantity of fuel injected. Since modern diesel engines operate on precise multiple injection strategies in order to maximize efficiency and performance of combustion, IDIDs can have a serious adverse effect on engine operation and vehicle drivability.
  • IDIDs are formed from when the hydrophilic-lipophilic balance (HLB) of sparingly soluble contaminants moves to a level where the hydrophilic head group dominates over the lipophilic tail. As the length of the lipophilic tail decreases, the hydrophilic head group begins to dominate. The structure of the tail (branched versus linear) and/or may also affect the solubility of the contaminants. In addition, as the polarity of the head group sparingly soluble contaminants increase, its solubility decreases.
  • HLB hydrophilic-lipophilic balance
  • metal soap IDIDs is dependent upon the size (number of carbons) of the hydrocarbon tail of the "soap" and the number of carboxylic acids groups (CO 2 H) in the head group of the corrosion inhibitor. It was observed that the tendency to form deposits increases when the inhibitor had a short tail and multiple carboxylic acids in the head group. In other words, dicarboxylic acid corrosion inhibitors with a lower number average molecular weight (M n ) ranging between 280 and 340, have a greater tendency to form sodium soap deposits than corrosion inhibitors with a higher number average molecular weight. Persons of ordinary skill in the art will understand that there may be some low molecular weight polymers present in corrosion inhibitors with a number average molecular weight above 340.
  • Amide lacquer formation is less certain but it has been suggested that it is derived from polyisobutylene succinimides (PIBSIs) with low number average molecular weight (M n ) which are added to diesel fuel to control nozzle fouling.
  • PIBSIs polyisobutylene succinimides
  • M n number average molecular weight
  • Low molecular weight PIBSIs may have an average M n of 400 or less using gel permeation chromatography (GPC) and a polystyrene calibration curve.
  • GPC gel permeation chromatography
  • low M n PIBSIs may have an average M n of 200 to 300.
  • These low molecular weight PIBSIs may be byproducts formed from low molecular weight PIBS present in the production process.
  • amide lacquer IDIDs have been shown to be linked to low molecular weight species by demonstrating that amide lacquer IDIDs can be produced in US Tier 3-compliant engines using a low molecular weight PIBSI fraction.
  • laboratory tests have shown that as little as 5 ppm of the low molecular weight PIBSI can cause deposit issues and it is possible that real world concentrations may be lower with deposits occurring over longer periods of time, such as from 0.01 to 5 ppm low molecular weight PIBSI.
  • Such low molecular weight PIBSI fractions can be represented, for example, by structure: wherein R* is as defined above, and R** is a hydrocarbyl polyamine such as an ethylene polyamine.
  • a method of reducing and/or preventing internal diesel injector deposits may comprise employing a fuel composition comprising the imide quat as described above.
  • the fuel may have a low molecular weight soap present therein.
  • the low molecular weight soap can be derived from the presence of from 0.01 to 5 ppm of a metal and 1 to 12, or 1 to 8, or 8 to 12 ppm of a corrosion inhibitor.
  • Exemplary metals include, but are not limited to, sodium, calcium, and potassium.
  • the corrosion inhibitors may comprise an alkenyl succinic acid such as dodecenyl succinic acid (DDSA) or hexadecenyl succinic acid (HDSA).
  • the fuel composition may have a low molecular weight polyisobutylene succinimides (PIBSI) present therein.
  • PIBSI polyisobutylene succinimides
  • the low molecular weight PIBSI may be present in the fuel at greater than 0.01 ppm, such as, for example, 5 to 25 ppm, or from 0.01 to 5 ppm of a low molecular weight PIBSI.
  • the technology may include a method of cleaning-up deposits in a diesel engine, such as, a diesel engine having a high pressure (i.e., above 35MPa) common rail injector system, by operating the engine with a fuel containing an imide quat therein.
  • the clean-up method includes reducing and/or preventing IDID causing deposits derived from the presence of a low molecular weight soap.
  • the clean-up method includes reducing and/or preventing IDID causing deposits derived from the presence of a low molecular weight PIBSI.
  • 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.
  • a 1000 number average molecular weight (M n ) polyisobutylene (PIB) (2000 g., 2.0 moles, high-vinylidene PIB) having greater than 70 % vinylidene groups is charged to a 5-liter flange flask equipped with overhead stirrer, air condenser, nitrogen inlet, thermocouple and EurothermTM temperature controller (reaction kit).
  • the reaction kit is then reconfigured for vacuum stripping.
  • the batch is stripped at 203 °C and 0.05 bar to remove unreacted maleic anhydride.
  • the batch comprising the formed PIBSA is then cooled back to 50 °C and decanted into a storage vessel.
  • a 1000 M n PIBSA (1950.3g, 1.86 moles) product of Example 1 is charged to a 3-liter flask equipped with a water condenser and Dean Stark trap, a thermocouple, a dropping funnel, an overhead stirrer and Nitrogen inlet and heated to 90 °C.
  • DMAPA Dimethylaminopropylamine (189.7g, 1.86 moles) DMAPA is added to the flask via the dropping funnel over 50 minutes. The batch temperature is kept below 120 °C while adding the DMAPA.
  • the reaction is slowly heated to 150 °C and maintained at that temperature for 3 hours. Approximately 40 g of water is collected in the Dean Stark apparatus while heating. The remaining product is the 1000 M n PIBSA/DMAPA quaternizable compound.
  • a 1000 M n PIBSA/DMAPA quaternizable compound (551.1g, 0.54 moles, as prepared in Example 2) is added to a 1-liter flask equipped with a water condenser, a thermocouple, a syringe pump, an overhead stirrer and nitrogen inlet.
  • 2-ethylhexanol (124.5g, 0.96 moles), acetic acid (32.4g, 0.54 moles) and water (5.0g, 0.287 moles) are also charged to the 1-liter flask.
  • the batch is then heated to 75 °C, under agitation and nitrogen atmosphere.
  • Propylene oxide is added via a syringe pump over 4 hours.
  • the batch is then held for 4 hours at 75 °C before being cooled back to 50 °C.
  • the imide/propylene oxide quat is then decanted into a storage vessel.
  • a 1000 M n PIBSA/DMAPA quaternizable compound (476.2, 0.47 moles, as prepared in Example 2) is added to a 1-liter flask flange flask equipped with a water condenser, a thermocouple, a syringe pump, an overhead stirrer and a nitrogen inlet.
  • a 1000 M n PIBSA/DMAPA quaternizable compound (791.4 g, 0.776 moles, as prepared in Example 2) is added to a 2-liter flask flange flask equipped with a water condenser, a thermocouple, an overhead stirrer and a nitrogen inlet.
  • Example 6 Formation of a 1000 M n PIBSA/DMAPA Quaternary Ammonium Salt using 1,2-Epoxyhexadecane (an imide/epoxyhexadecane quat)
  • a 1000 M n PIBSA/DMAPA quaternizable compound (500 g, 0.495 moles, as prepared in Example 2) is added to a 1-liter flask flange flask equipped with a water condenser, a thermocouple, an overhead stirrer and a nitrogen inlet.
  • 2-ethylhexanol (163.34 g, 1.26 moles) and water (5 g, 0.27 moles) are added to the flask and heated to 90 °C.
  • Acetic acid (29.65, 0.494 moles) and 1,2-epoxyhexadecane (118.71 g, 0.494 moles) are added to the flask.
  • Agitation is then initiated (200 rpm) and a slow nitrogen purge is introduced.
  • the batch is held at 90 °C for 3 hours.
  • the imide/epoxyhexadecane quat is then then cooled before it is transferred into a storage vessel.
  • a 550 number average molecular weight (M n ) polyisobutylene (PIB) (2840 g, 5.163 moles, mid-vinylidene PIB available from Daelim) having greater than 20 % vinylidene groups is charged to a 5-liter flange flask equipped with overhead stirrer, air condenser, nitrogen inlet, thermocouple and EurothermTM temperature controller (reaction kit).
  • M n number average molecular weight polyisobutylene
  • the 550 M n PIBSA (1556.2 g, 2.29 moles) (product of Example 8) is charged to a 3-liter flask equipped with a water condenser and Dean Stark trap, a thermocouple, a dropping funnel, an overhead stirrer and Nitrogen inlet and heated to 90 °C.
  • DMAPA (233.4 g, 2.29moles) is added to the flask via the dropping funnel over 50 minutes.
  • the batch temperature is kept below 120 °C while adding the DMAPA.
  • the reaction is slowly heated to 150 °C and maintained at that temperature for 3 hours. Approximately 40g of water is collected in the Dean Stark apparatus while heating. The remaining product is the 550 M n PIBSA/DMAPA quaternizable compound.
  • Example 10 (prophetic) - Formation of a 550 M n PIBSA/DMAPA Quaternary Ammonium Salt using 1,2-Epoxybutane (an imide/epoxybutane quat)
  • the 550 M n PIBSA/DMAPA quaternizable compound of Example 9 (470 g, 0.61 moles) is added to a 1-liter flask flange flask equipped with a water condenser, a thermocouple, an overhead stirrer and a nitrogen inlet.
  • 2-ethylhexanol (136 g, 1.05 moles), 1,2-epoxydodecane (114.1 g, 0.62 moles), acetic acid (37 g, 0.62 moles), and water (4.4 g, 0.24 moles) are also charged to the 1-liter flask.
  • the batch is then heated to 75 °C under agitation and nitrogen and maintained at temperature for 3 hours.
  • the imide/epoxydodecane quat is then then cooled before it is transferred into a storage vessel.
  • Example 12 (prophetic) - Formation of a 550 M n PIBSA/DMAPA Quaternary Ammonium Salt using 1,2-Epoxyhexadecane (an imide/epoxyhexadecane quat)
  • the 550 M n PIBSA/DMAPA quaternizable compound of Example 9 (470 g, 0.61 moles) is added to a 1-liter flask flange flask equipped with a water condenser, a thermocouple, an overhead stirrer and a nitrogen inlet.
  • 2-ethylhexanol (136 g, 1.05 moles), 1,2-epoxyhexadecane (148.99 g, 0.62 moles), acetic acid (37.0 g, 0.62 moles), and water (4.4 g, 0.24 moles) are added to the flask and heated to 75 °C while agitating under nitrogen. The batch is held at 75 °C for 3 hours. The imide/epoxyhexadecane quat is then then cooled before it is transferred into a storage vessel.
  • Example 13 (prophetic) - Formation of a 550 M n PIBSA/DMAPA Quaternary Ammonium Salt using Glycidol (an imide/glycidol quat)
  • the 550 M n PIBSA/DMAPA quaternizable compound of Example 9 (471 g, 0.62 moles) is added to a 1-liter flask flange flask equipped with a water condenser, a thermocouple, an overhead stirrer and a nitrogen inlet.
  • a 2300 number average molecular weight (M n ) polyisobutylene (PIB) (2000 g., 0.87 moles) high-vinylidene PIB having greater than 20 % vinylidene groups is charged to a 5-liter flange flask equipped with overhead stirrer, air condenser, nitrogen inlet, thermocouple and EurothermTM temperature controller (reaction kit).
  • M n number average molecular weight
  • PIB polyisobutylene
  • the reaction kit is then reconfigured for vacuum stripping.
  • the batch is stripped at 203 °C and 0.05 bar to remove unreacted maleic anhydride.
  • Diluent oil such as mineral oil (1116.8 g) is added to the batch.
  • the batch comprising the formed PIBSA is then cooled back to 50 °C and decanted into a storage vessel.
  • a 2300 M n PIBSA (3000 g, 1.52 moles, as prepared in Example 14) is charged to a 5-liter flask equipped with a water condenser and Dean Stark trap, a thermocouple, a dropping funnel, an overhead stirrer and Nitrogen inlet and heated to 90 °C.
  • DMAPA (154.72 g, 1.517 moles) is added to the flask via the dropping funnel over 40 minutes. An exotherm increasing 6 °C was observed. Once all the DMAPA is added, the reaction is slowly heated to 150 °C and maintained at that temperature for 3 hours, and approximately 25g water is collected in Dean Stark trap. The resulting product is a 2300 M n PIBSA/DMAPA quaternizable compound.
  • Example 16 (prophetic) - Formation of a 2300 M n PIBSA/DMAPA Quaternary Ammonium Salt using 1,2-Epoxydodecane (an imide/epoxydodecane quat)
  • the 2300 M n PIBSA/DMAPA quaternizable compound of Example 15 (550.8 g, 0.29 moles) is added to a 1-liter flask flange flask equipped with a water condenser, a thermocouple, an overhead stirrer and a nitrogen inlet.
  • the 2300 M n PIBSA/DMAPA quaternizable compound of Example 15 (550.8 g, 0.29 moles) is added to a 1-liter flask flange flask equipped with a water condenser, a thermocouple, an overhead stirrer and a nitrogen inlet.
  • the demulsification test is performed to measure the epoxide quats' ability to demulsify fuel and water mixtures as compared to the 1000 M n imide/propylene oxide quat of Comparative Example 3.
  • the demulsification test is run according to the procedure in ASTM D1094-07 ("Standard Test Method for Water Reaction of Aviation Fuels").
  • the quaternary ammonium salt is added to room temperature fuel at 60 ppm actives by weight based on a total weight of the fuel.
  • a commercially available demulsifier (Tolad 9327 available from Baker Hughes) is added to the fuel at 18 ppm by weight based on a total weight of the fuel.
  • Table 2 and FIG. 2 and in Table 3 and FIG. 3 The results of the deposit tests for the first and second sets are shown in Table 2 and FIG. 2 and in Table 3 and FIG. 3 respectively.
  • Table 2 - 10 ppm Actives Flow Loss (%) Flow Remaining (%) Example 4 65.5 34.5
  • Example 5 72.1 27.9
  • Example 7 70.5 29.5
  • Reference Fuel 80 20
  • Table 3 - 30 ppm Actives Flow Loss (%) Flow Remaining (%)
  • Example 18 19.0 81.0 Reference Fuel 80 20 The results of the deposit tests for the first and second sets are shown in Table 2 and FIG. 2 and in Table 3 and FIG. 3 respectively.
  • Table 2 - 10 ppm Actives Flow Loss (%) Flow Remaining (%)
  • Example 4 65.5 34.5
  • Example 5 72.1 27.9
  • Example 7 70.5 29.5
  • Reference Fuel 80 20
  • Table 3 - 30 pp
  • the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases “consisting essentially of' and “consisting of,” where “consisting of' excludes any element or step not specified and “consisting essentially of' permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

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US11008526B2 (en) * 2019-07-23 2021-05-18 Croda Inc. Demulsifier for quaternary ammonium salt containing fuels
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Citations (148)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2501731A (en) 1946-10-14 1950-03-28 Union Oil Co Modified lubricating oil
US2616905A (en) 1952-03-13 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes and methods of making same
US2616925A (en) 1951-03-16 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes formed by use of thiophosphoric promoters
US2616911A (en) 1951-03-16 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes formed by use of sulfonic promoters
US2777874A (en) 1952-11-03 1957-01-15 Lubrizol Corp Metal complexes and methods of making same
US3036003A (en) 1957-08-07 1962-05-22 Sinclair Research Inc Lubricating oil composition
US3087436A (en) 1960-12-02 1963-04-30 Ross Gear And Tool Company Inc Hydraulic pump
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3215707A (en) 1960-06-07 1965-11-02 Lubrizol Corp Lubricant
US3231587A (en) 1960-06-07 1966-01-25 Lubrizol Corp Process for the preparation of substituted succinic acid compounds
US3236770A (en) 1960-09-28 1966-02-22 Sinclair Research Inc Transaxle lubricant
US3256186A (en) 1963-02-12 1966-06-14 Lubrizol Corp Process for producing carbonated basic metal compositions
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3316177A (en) 1964-12-07 1967-04-25 Lubrizol Corp Functional fluid containing a sludge inhibiting detergent comprising the polyamine salt of the reaction product of maleic anhydride and an oxidized interpolymer of propylene and ethylene
US3318809A (en) 1965-07-13 1967-05-09 Bray Oil Co Counter current carbonation process
US3320162A (en) 1964-05-22 1967-05-16 Phillips Petroleum Co Increasing the base number of calcium petroleum sulfonate
US3340281A (en) 1965-06-14 1967-09-05 Standard Oil Co Method for producing lubricating oil additives
US3351552A (en) 1964-09-08 1967-11-07 Lubrizol Corp Lithium compounds as rust inhibitors for lubricants
US3361673A (en) 1959-08-24 1968-01-02 Chevron Res Lubricating oil compositions containing alkenyl succinimides of tetraethylene pentamine
US3365396A (en) 1965-12-28 1968-01-23 Texaco Inc Overbased calcium sulfonate
US3381022A (en) 1963-04-23 1968-04-30 Lubrizol Corp Polymerized olefin substituted succinic acid esters
US3384585A (en) 1966-08-29 1968-05-21 Phillips Petroleum Co Overbasing lube oil additives
USRE26433E (en) 1963-12-11 1968-08-06 Amide and imide derivatives of metal salts of substituted succinic acids
US3401118A (en) 1967-09-15 1968-09-10 Chevron Res Preparation of mixed alkenyl succinimides
US3414347A (en) 1965-03-30 1968-12-03 Edroy Products Company Inc Binocular with pivoted lens plate
US3433744A (en) 1966-11-03 1969-03-18 Lubrizol Corp Reaction product of phosphosulfurized hydrocarbon and alkylene polycarboxylic acid or acid derivatives and lubricating oil containing the same
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
US3448047A (en) 1967-04-05 1969-06-03 Standard Oil Co Lube oil dispersants
US3461172A (en) 1966-11-22 1969-08-12 Consolidation Coal Co Hydrogenation of ortho-phenolic mannich bases
US3467668A (en) 1965-04-27 1969-09-16 Roehm & Haas Gmbh Polyamines comprising ethylene and imidazolinyl groups
US3488284A (en) 1959-12-10 1970-01-06 Lubrizol Corp Organic metal compositions and methods of preparing same
US3501405A (en) 1967-08-11 1970-03-17 Rohm & Haas Lubricating and fuel compositions comprising copolymers of n-substituted formamide-containing unsaturated esters
US3539633A (en) 1965-10-22 1970-11-10 Standard Oil Co Di-hydroxybenzyl polyamines
US3542680A (en) 1963-04-23 1970-11-24 Lubrizol Corp Oil-soluble carboxylic acid phenol esters and lubricants and fuels containing the same
US3576743A (en) 1969-04-11 1971-04-27 Lubrizol Corp Lubricant and fuel additives and process for making the additives
US3586629A (en) 1968-09-16 1971-06-22 Mobil Oil Corp Metal salts as lubricant additives
US3591598A (en) 1968-11-08 1971-07-06 Standard Oil Co Certain condensation products derived from mannich bases
US3598738A (en) 1966-09-23 1971-08-10 Du Pont Oil compositions containing ethylene copolymers
US3629109A (en) 1968-12-19 1971-12-21 Lubrizol Corp Basic magnesium salts processes and lubricants and fuels containing the same
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
US3634515A (en) 1968-11-08 1972-01-11 Standard Oil Co Alkylene polyamide formaldehyde
US3725480A (en) 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3726882A (en) 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3778371A (en) 1972-05-19 1973-12-11 Ethyl Corp Lubricant and fuel compositions
US3912764A (en) 1972-09-29 1975-10-14 Cooper Edwin Inc Preparation of alkenyl succinic anhydrides
US3954808A (en) 1972-11-02 1976-05-04 Edwin Cooper & Company Limited Methylene bis-phenol alkanoic acid compounds
US3980569A (en) 1974-03-15 1976-09-14 The Lubrizol Corporation Dispersants and process for their preparation
US4026809A (en) 1974-12-19 1977-05-31 Texaco Inc. Lubricating compositions containing methacrylate ester graft copolymers as useful viscosity index improvers
US4032700A (en) 1973-06-25 1977-06-28 Exxon Research And Engineering Company Process for the preparation of aminated polymers useful as additives for fuels and lubricants
US4110349A (en) 1976-06-11 1978-08-29 The Lubrizol Corporation Two-step method for the alkenylation of maleic anhydride and related compounds
US4137185A (en) 1977-07-28 1979-01-30 Exxon Research & Engineering Co. Stabilized imide graft of ethylene copolymeric additives for lubricants
US4156061A (en) 1974-03-06 1979-05-22 Exxon Research & Engineering Co. Epoxidized terpolymer or derivatives thereof, and oil and fuel compositions containing same
US4171959A (en) 1977-12-14 1979-10-23 Texaco Inc. Fuel composition containing quaternary ammonium salts of succinimides
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4253980A (en) 1979-06-28 1981-03-03 Texaco Inc. Quaternary ammonium salt of ester-lactone and hydrocarbon oil containing same
US4320019A (en) 1978-04-17 1982-03-16 The Lubrizol Corporation Multi-purpose additive compositions and concentrates containing same
US4326973A (en) 1981-01-13 1982-04-27 Texaco Inc. Quaternary ammonium succinimide salt composition and lubricating oil containing same
US4338206A (en) 1981-03-23 1982-07-06 Texaco Inc. Quaternary ammonium succinimide salt composition and lubricating oil containing same
EP0061895A2 (fr) 1981-03-31 1982-10-06 Exxon Research And Engineering Company Additif pour améliorer l'écoulement des carburants distillés et leurs concentrats
US4357250A (en) 1978-04-17 1982-11-02 The Lubrizol Corporation Nitrogen-containing terpolymer-based compositions useful as multi-purpose lubricant additives
US4491455A (en) 1982-02-10 1985-01-01 Nippon Oil And Fats Co., Ltd. Method for improving cold flow of fuel oils
CA1183125A (fr) 1981-09-10 1985-02-26 Daniel E. Barrer Compositions, concentres, lubrifiants et methodes pour reduire la consommation de carburant des moteurs a combustion interne
EP0183478A2 (fr) * 1984-11-21 1986-06-04 Chevron Research Company Succinimides modifiés avec glycidole
US4627928A (en) 1976-08-26 1986-12-09 The Lubrizol Corporation Basic non-carbonated magnesium compositions and fuel, lubricant and additive concentrate compositions containing same
US4654403A (en) 1985-03-25 1987-03-31 The Lubrizol Corporation Polymeric compositions comprising olefin polymer and nitrogen containing ester of a carboxy interpolymer
US4658078A (en) 1986-08-15 1987-04-14 Shell Oil Company Vinylidene olefin process
US4668834A (en) 1985-10-16 1987-05-26 Uniroyal Chemical Company, Inc. Low molecular weight ethylene-alphaolefin copolymer intermediates
EP0261957A2 (fr) 1986-09-24 1988-03-30 Exxon Chemical Patents Inc. Compositions chimiques et usage comme additifs de combustibles
EP0279863A1 (fr) 1986-08-26 1988-08-31 Mitsui Chemicals, Inc. Catalyseur de polymerisation d'alpha-olefine et procede de polymerisation
US4863623A (en) 1988-03-24 1989-09-05 Texaco Inc. Novel VI improver, dispersant, and anti-oxidant additive and lubricating oil composition containing same
EP0355895A2 (fr) 1988-08-05 1990-02-28 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de dérivés de l'anhydride succinique
US4937299A (en) 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
US5071919A (en) 1990-05-17 1991-12-10 Ethyl Petroleum Additives, Inc. Substituted acylating agents and their production
US5137980A (en) 1990-05-17 1992-08-11 Ethyl Petroleum Additives, Inc. Ashless dispersants formed from substituted acylating agents and their production and use
US5137978A (en) 1990-05-17 1992-08-11 Ethyl Petroleum Additives, Inc. Substituted acylating agents and their production
US5254138A (en) 1991-05-03 1993-10-19 Uop Fuel composition containing a quaternary ammonium salt
US5286823A (en) 1991-06-22 1994-02-15 Basf Aktiengesellschaft Preparation of highly reactive polyisobutenes
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
US5336278A (en) 1993-05-13 1994-08-09 The Lubrizol Corporation Fuel composition containing an aromatic amide detergent
US5342505A (en) * 1993-02-25 1994-08-30 Betz Laboratories, Inc. Use of polyalkenyl succinimides-glycidol reaction products as antifoulants in hydrocarbon process media
US5458793A (en) 1993-05-13 1995-10-17 The Lubrizol Corporation Compositions useful as additives for lubricants and liquid fuels
US5620949A (en) 1995-12-13 1997-04-15 The Lubrizol Corporation Condensation products of alkylphenols and aldehydes, and derivatives thereof
US5688751A (en) 1996-08-14 1997-11-18 The Lubrizol Corporation Salicylate salts as lubricant additives for two-cycle engines
WO1998004656A1 (fr) 1996-07-31 1998-02-05 Elf Antar France Carburant pour moteurs diesel a faible teneur en soufre
US5739356A (en) 1995-08-22 1998-04-14 The Lubrizol Corporation Lactones useful as intermediates for preparing lubricating oil and fuel additives
US5777142A (en) 1995-08-22 1998-07-07 The Lubrizol Corporation Unsaturated hydroxycarboxylic compounds useful as intermediates for preparing lubricant and fuel additives
US5827805A (en) 1996-02-29 1998-10-27 The Lubrizol Corporation Condensates of alkyl phenols and glyoxal and products derived therefrom
US5840920A (en) 1996-08-08 1998-11-24 The Lubrizol Corporation Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives
US5851966A (en) 1997-06-05 1998-12-22 The Lubrizol Corporation Reaction products of substituted carboxylic acylating agents and carboxylic reactants for use in fuels and lubricants
US5885944A (en) 1996-05-21 1999-03-23 The Lubrizol Corporation Low chlorine polyalkylene substituted carboxylic acylating agent compositions and compounds derived therefrom
US5912213A (en) 1997-06-05 1999-06-15 The Lubrizol Corporation Substituted carboxylic acylating agent compositions and derivatives thereof for use in lubricants and fuels
US6001781A (en) 1997-09-10 1999-12-14 The Lubrizol Corporation Process for preparing condensation product of hydroxy-substituted aromatic compounds and glyoxylic reactants
US6020500A (en) 1995-08-22 2000-02-01 The Lubrizol Corporation Hydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives
US6077909A (en) 1997-02-13 2000-06-20 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
WO2000044857A2 (fr) 1998-12-11 2000-08-03 Infineum Usa Lp Materiaux macromoleculaires
US6107257A (en) 1997-12-09 2000-08-22 Ethyl Corporation Highly grafted, multi-functional olefin copolymer VI modifiers
US6107258A (en) 1997-10-15 2000-08-22 Ethyl Corporation Functionalized olefin copolymer additives
US6117825A (en) 1992-05-07 2000-09-12 Ethyl Corporation Polyisobutylene succinimide and ethylene-propylene succinimide synergistic additives for lubricating oils compositions
US6147036A (en) 1996-08-08 2000-11-14 The Lubrizol Corporation Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives and derivatives thereof
US6153565A (en) 1996-05-31 2000-11-28 Exxon Chemical Patents Inc Overbased metal-containing detergents
US6165235A (en) 1997-08-26 2000-12-26 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
US6200936B1 (en) 1997-11-13 2001-03-13 The Lubrizol Corporation Salicyclic calixarenes and their use as lubricant additives
US6281179B1 (en) 1996-05-31 2001-08-28 Infineum Usa L.P. Process for preparing an overbased metal-containing detergents
US6429178B1 (en) 1996-05-31 2002-08-06 Infineum Usa L.P. Calcium overbased metal-containing detergents
US6429179B1 (en) 1996-05-31 2002-08-06 Infineum U.S.A. L.P. Calcium overbased metal-containing detergents
US6559105B2 (en) 2000-04-03 2003-05-06 The Lubrizol Corporation Lubricant compositions containing ester-substituted hindered phenol antioxidants
US6562913B1 (en) 1999-09-16 2003-05-13 Texas Petrochemicals Lp Process for producing high vinylidene polyisobutylene
WO2004035715A1 (fr) 2002-10-14 2004-04-29 Basf Aktiengesellschaft Utilisation d'homopolymères d'éther vinylique hydrocarbyle pour améliorer l'effet de promoteurs d'écoulement à froid
US6743266B2 (en) 2000-03-31 2004-06-01 Texaco, Inc. Fuel additive composition for improving delivery of friction modifier
US20040176552A1 (en) 2001-03-28 2004-09-09 Texas Petrochemicals Lp Process for producing mid-range vinylidene content polyisobutylene polymer products
US20050065045A1 (en) 2001-11-05 2005-03-24 Wilk Melody A. Sulfonate detergent system for improved fuel economy
WO2005054314A2 (fr) 2003-12-04 2005-06-16 Basf Aktiengesellschaft Compositions d'huiles combustibles presentant de meilleures proprietes d'ecoulement a froid
US20050198894A1 (en) 2004-03-11 2005-09-15 Crompton Corporation Lubricant and fuel compositions containing hydroxy carboxylic acid and hydroxy polycarboxylic acid esters
US20060014651A1 (en) 2004-07-19 2006-01-19 Esche Carl K Jr Additives and lubricant formulations for improved antiwear properties
WO2006015130A1 (fr) 2004-07-30 2006-02-09 The Lubrizol Corporation Modifiants de viscosité de dispersant contenant des amines aromatiques
WO2006044411A1 (fr) 2004-10-12 2006-04-27 The Lubrizol Corporation Dérivés d’acide tartarique permettant d’augmenter les économies de combustible et jouant le rôle d’agents anti-usure dans les huiles de carter, et préparations basées sur lesdits dérivés
US7238650B2 (en) 2002-06-27 2007-07-03 The Lubrizol Corporation Low-chlorine, polyolefin-substituted, with amine reacted, alpha-beta unsaturated carboxylic compounds
US20080113890A1 (en) 2006-11-09 2008-05-15 The Lubrizol Corporation Quaternary Ammonium Salt of a Polyalkene-Substituted Amine Compound
US20080119378A1 (en) 2006-11-21 2008-05-22 Chevron Oronite Company Llc Functional fluids comprising alkyl toluene sulfonates
WO2008147704A1 (fr) 2007-05-24 2008-12-04 The Lubrizol Corporation Composition lubrifiante contenant un agent anti-usure
US20090054278A1 (en) 2005-02-18 2009-02-26 The Lubrizol Corporation Multifunctional Dispersants
US7615521B2 (en) 2003-08-01 2009-11-10 The Lubrizol Corporation Mixed dispersants for lubricants
WO2010014655A1 (fr) 2008-07-31 2010-02-04 The Lubrizol Corporation Nouveaux copolymères, et compositions lubrifiantes de ceux-ci
US7727943B2 (en) 2005-03-28 2010-06-01 The Lubrizol Corporation Titanium compounds and complexes as additives in lubricants
WO2011022317A1 (fr) 2009-08-18 2011-02-24 The Lubrizol Corporation Composition lubrifiante contenant un agent anti-usure
US7951211B2 (en) 2005-06-16 2011-05-31 The Lubrizol Corporation Quaternary ammonium salt detergents for use in fuels
WO2011095819A1 (fr) 2010-02-05 2011-08-11 Innospec Limited Compositions de carburant
WO2011110860A1 (fr) 2010-03-10 2011-09-15 Innospec Limited Composition de carburant comprenant un additif détergent et un additif sel d'ammonium quaternaire
US20110219674A1 (en) 2008-10-10 2011-09-15 The Lubrizol Corporation Additives to Reduce Metal Pick-Up in Fuels
US20110258917A1 (en) 2010-04-27 2011-10-27 Basf Se Quaternized terpolymer
WO2011141731A1 (fr) 2010-05-10 2011-11-17 Innospec Limited Composition, procédé et utilisation
US8083814B2 (en) 2006-09-01 2011-12-27 The Lubrizol Corporation Quaternary ammonium salt of a mannich compound
US20110315107A1 (en) 2010-06-25 2011-12-29 Basf Se Quaternized copolymer
WO2012004300A1 (fr) * 2010-07-06 2012-01-12 Basf Se Composés azotés quaternisés exempts d'acide et utilisation desdits composés comme additifs pour carburants ou pour lubrifiants
US20120010112A1 (en) 2010-07-06 2012-01-12 Basf Se Acid-free quaternized nitrogen compounds and use thereof as additives in fuels and lubricants
US20120149617A1 (en) 2010-12-09 2012-06-14 Basf Se Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines and use thereof as a fuel additive or lubricant additive
US20120255512A1 (en) 2008-05-13 2012-10-11 Afton Chemical Corporation Fuel additives for treating internal deposits of fuel injectors
WO2013017886A1 (fr) 2011-08-03 2013-02-07 Innospec Limited Compositions de carburant
WO2013017884A1 (fr) 2011-08-03 2013-02-07 Innospec Limited Compositions de carburant
WO2013017889A1 (fr) 2011-08-03 2013-02-07 Innospec Limited Compositions de carburant
US20130074794A1 (en) 2011-09-22 2013-03-28 Afton Chemical Corporation Fuel additives for treating internal deposits of fuel injectors
WO2013070503A1 (fr) 2011-11-11 2013-05-16 Afton Chemical Corporation Additif pour carburant pour un meilleur rendement des moteurs à injection directe du carburant
US20130118062A1 (en) 2011-11-11 2013-05-16 Afton Chemical Corporation Fuel additive for improved performance of direct fuel injected engines
US20130133243A1 (en) 2011-06-28 2013-05-30 Basf Se Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants
US20130225463A1 (en) 2011-11-04 2013-08-29 Markus Hansch Quaternized polyether amines and their use as additive for fuels and lubricants
US20130312318A1 (en) * 2012-05-25 2013-11-28 Basf Se Use of a reaction product of carboxylic acids with aliphatic polyamines for improving or boosting the separation of water from fuel oils
US20130333649A1 (en) 2012-06-13 2013-12-19 Afton Chemical Corporation Fuel additive for improved performance in fuel injected engines
WO2014007379A1 (fr) * 2012-07-05 2014-01-09 Ｊｘ日鉱日石エネルギー株式会社 Composé succinimide, additif pour huile lubrifiante et composition d'huile lubrifiante

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120065112A1 (en) * 2008-03-31 2012-03-15 Exxonmobil Research And Engineering Company Lubricant composition with improved varnish deposit resistance
NO2430131T3 (fr) * 2009-05-15 2018-02-03
US9044677B2 (en) * 2011-07-11 2015-06-02 Roblox Corporation System for optimizing processing capacity for a group of gaming appliances engaged in play of an online game
US8690970B2 (en) * 2012-02-24 2014-04-08 Afton Chemical Corporation Fuel additive for improved performance in fuel injected engines
EP2912148A1 (fr) * 2012-10-23 2015-09-02 The Lubrizol Corporation Détergent pour diesel sans surcharge de faible poids moléculaire
US8992636B1 (en) * 2013-10-08 2015-03-31 Afton Chemical Corporation Alkoxylated quaternary ammonium salts and fuels containing them
US9464252B2 (en) * 2013-10-08 2016-10-11 Afton Chemical Corporation Quaternary ammonium detergent fuel additives

Patent Citations (164)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2501731A (en) 1946-10-14 1950-03-28 Union Oil Co Modified lubricating oil
US2616925A (en) 1951-03-16 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes formed by use of thiophosphoric promoters
US2616911A (en) 1951-03-16 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes formed by use of sulfonic promoters
US2616905A (en) 1952-03-13 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes and methods of making same
US2777874A (en) 1952-11-03 1957-01-15 Lubrizol Corp Metal complexes and methods of making same
US3036003A (en) 1957-08-07 1962-05-22 Sinclair Research Inc Lubricating oil composition
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
US3219666A (en) 1959-03-30 1965-11-23 Derivatives of succinic acids and nitrogen compounds
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3361673A (en) 1959-08-24 1968-01-02 Chevron Res Lubricating oil compositions containing alkenyl succinimides of tetraethylene pentamine
US3488284A (en) 1959-12-10 1970-01-06 Lubrizol Corp Organic metal compositions and methods of preparing same
US3215707A (en) 1960-06-07 1965-11-02 Lubrizol Corp Lubricant
US3231587A (en) 1960-06-07 1966-01-25 Lubrizol Corp Process for the preparation of substituted succinic acid compounds
US3236770A (en) 1960-09-28 1966-02-22 Sinclair Research Inc Transaxle lubricant
US3087436A (en) 1960-12-02 1963-04-30 Ross Gear And Tool Company Inc Hydraulic pump
US3256186A (en) 1963-02-12 1966-06-14 Lubrizol Corp Process for producing carbonated basic metal compositions
US3542680A (en) 1963-04-23 1970-11-24 Lubrizol Corp Oil-soluble carboxylic acid phenol esters and lubricants and fuels containing the same
US3381022A (en) 1963-04-23 1968-04-30 Lubrizol Corp Polymerized olefin substituted succinic acid esters
USRE26433E (en) 1963-12-11 1968-08-06 Amide and imide derivatives of metal salts of substituted succinic acids
US3320162A (en) 1964-05-22 1967-05-16 Phillips Petroleum Co Increasing the base number of calcium petroleum sulfonate
US3351552A (en) 1964-09-08 1967-11-07 Lubrizol Corp Lithium compounds as rust inhibitors for lubricants
US3316177A (en) 1964-12-07 1967-04-25 Lubrizol Corp Functional fluid containing a sludge inhibiting detergent comprising the polyamine salt of the reaction product of maleic anhydride and an oxidized interpolymer of propylene and ethylene
US3414347A (en) 1965-03-30 1968-12-03 Edroy Products Company Inc Binocular with pivoted lens plate
US3467668A (en) 1965-04-27 1969-09-16 Roehm & Haas Gmbh Polyamines comprising ethylene and imidazolinyl groups
US3340281A (en) 1965-06-14 1967-09-05 Standard Oil Co Method for producing lubricating oil additives
US3318809A (en) 1965-07-13 1967-05-09 Bray Oil Co Counter current carbonation process
US3539633A (en) 1965-10-22 1970-11-10 Standard Oil Co Di-hydroxybenzyl polyamines
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3365396A (en) 1965-12-28 1968-01-23 Texaco Inc Overbased calcium sulfonate
US3384585A (en) 1966-08-29 1968-05-21 Phillips Petroleum Co Overbasing lube oil additives
US3598738A (en) 1966-09-23 1971-08-10 Du Pont Oil compositions containing ethylene copolymers
US3433744A (en) 1966-11-03 1969-03-18 Lubrizol Corp Reaction product of phosphosulfurized hydrocarbon and alkylene polycarboxylic acid or acid derivatives and lubricating oil containing the same
US3461172A (en) 1966-11-22 1969-08-12 Consolidation Coal Co Hydrogenation of ortho-phenolic mannich bases
US3448047A (en) 1967-04-05 1969-06-03 Standard Oil Co Lube oil dispersants
US3501405A (en) 1967-08-11 1970-03-17 Rohm & Haas Lubricating and fuel compositions comprising copolymers of n-substituted formamide-containing unsaturated esters
US3401118A (en) 1967-09-15 1968-09-10 Chevron Res Preparation of mixed alkenyl succinimides
US3586629A (en) 1968-09-16 1971-06-22 Mobil Oil Corp Metal salts as lubricant additives
US3591598A (en) 1968-11-08 1971-07-06 Standard Oil Co Certain condensation products derived from mannich bases
US3634515A (en) 1968-11-08 1972-01-11 Standard Oil Co Alkylene polyamide formaldehyde
US3725480A (en) 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3726882A (en) 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3629109A (en) 1968-12-19 1971-12-21 Lubrizol Corp Basic magnesium salts processes and lubricants and fuels containing the same
US3576743A (en) 1969-04-11 1971-04-27 Lubrizol Corp Lubricant and fuel additives and process for making the additives
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
US3778371A (en) 1972-05-19 1973-12-11 Ethyl Corp Lubricant and fuel compositions
US3912764A (en) 1972-09-29 1975-10-14 Cooper Edwin Inc Preparation of alkenyl succinic anhydrides
US3954808A (en) 1972-11-02 1976-05-04 Edwin Cooper & Company Limited Methylene bis-phenol alkanoic acid compounds
US4032700A (en) 1973-06-25 1977-06-28 Exxon Research And Engineering Company Process for the preparation of aminated polymers useful as additives for fuels and lubricants
US4156061A (en) 1974-03-06 1979-05-22 Exxon Research & Engineering Co. Epoxidized terpolymer or derivatives thereof, and oil and fuel compositions containing same
US3980569A (en) 1974-03-15 1976-09-14 The Lubrizol Corporation Dispersants and process for their preparation
US4026809A (en) 1974-12-19 1977-05-31 Texaco Inc. Lubricating compositions containing methacrylate ester graft copolymers as useful viscosity index improvers
US4110349A (en) 1976-06-11 1978-08-29 The Lubrizol Corporation Two-step method for the alkenylation of maleic anhydride and related compounds
US4627928A (en) 1976-08-26 1986-12-09 The Lubrizol Corporation Basic non-carbonated magnesium compositions and fuel, lubricant and additive concentrate compositions containing same
US4137185A (en) 1977-07-28 1979-01-30 Exxon Research & Engineering Co. Stabilized imide graft of ethylene copolymeric additives for lubricants
US4171959A (en) 1977-12-14 1979-10-23 Texaco Inc. Fuel composition containing quaternary ammonium salts of succinimides
US4320019A (en) 1978-04-17 1982-03-16 The Lubrizol Corporation Multi-purpose additive compositions and concentrates containing same
US4357250A (en) 1978-04-17 1982-11-02 The Lubrizol Corporation Nitrogen-containing terpolymer-based compositions useful as multi-purpose lubricant additives
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4253980A (en) 1979-06-28 1981-03-03 Texaco Inc. Quaternary ammonium salt of ester-lactone and hydrocarbon oil containing same
US4326973A (en) 1981-01-13 1982-04-27 Texaco Inc. Quaternary ammonium succinimide salt composition and lubricating oil containing same
US4338206A (en) 1981-03-23 1982-07-06 Texaco Inc. Quaternary ammonium succinimide salt composition and lubricating oil containing same
EP0061895A2 (fr) 1981-03-31 1982-10-06 Exxon Research And Engineering Company Additif pour améliorer l'écoulement des carburants distillés et leurs concentrats
CA1183125A (fr) 1981-09-10 1985-02-26 Daniel E. Barrer Compositions, concentres, lubrifiants et methodes pour reduire la consommation de carburant des moteurs a combustion interne
US4491455A (en) 1982-02-10 1985-01-01 Nippon Oil And Fats Co., Ltd. Method for improving cold flow of fuel oils
US4937299A (en) 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
EP0183478A2 (fr) * 1984-11-21 1986-06-04 Chevron Research Company Succinimides modifiés avec glycidole
US4654403A (en) 1985-03-25 1987-03-31 The Lubrizol Corporation Polymeric compositions comprising olefin polymer and nitrogen containing ester of a carboxy interpolymer
US4668834A (en) 1985-10-16 1987-05-26 Uniroyal Chemical Company, Inc. Low molecular weight ethylene-alphaolefin copolymer intermediates
US4668834B1 (en) 1985-10-16 1996-05-07 Uniroyal Chem Co Inc Low molecular weight ethylene-alphaolefin copolymer intermediates
US4658078A (en) 1986-08-15 1987-04-14 Shell Oil Company Vinylidene olefin process
EP0279863A1 (fr) 1986-08-26 1988-08-31 Mitsui Chemicals, Inc. Catalyseur de polymerisation d'alpha-olefine et procede de polymerisation
EP0261957A2 (fr) 1986-09-24 1988-03-30 Exxon Chemical Patents Inc. Compositions chimiques et usage comme additifs de combustibles
US4863623A (en) 1988-03-24 1989-09-05 Texaco Inc. Novel VI improver, dispersant, and anti-oxidant additive and lubricating oil composition containing same
EP0355895A2 (fr) 1988-08-05 1990-02-28 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de dérivés de l'anhydride succinique
US5071919A (en) 1990-05-17 1991-12-10 Ethyl Petroleum Additives, Inc. Substituted acylating agents and their production
US5137980A (en) 1990-05-17 1992-08-11 Ethyl Petroleum Additives, Inc. Ashless dispersants formed from substituted acylating agents and their production and use
US5137978A (en) 1990-05-17 1992-08-11 Ethyl Petroleum Additives, Inc. Substituted acylating agents and their production
US5254138A (en) 1991-05-03 1993-10-19 Uop Fuel composition containing a quaternary ammonium salt
US5408018A (en) 1991-06-22 1995-04-18 Basf Aktiengesellschaft Preparation of highly reactive polyisobutenes
US5286823A (en) 1991-06-22 1994-02-15 Basf Aktiengesellschaft Preparation of highly reactive polyisobutenes
US6117825A (en) 1992-05-07 2000-09-12 Ethyl Corporation Polyisobutylene succinimide and ethylene-propylene succinimide synergistic additives for lubricating oils compositions
US5342505A (en) * 1993-02-25 1994-08-30 Betz Laboratories, Inc. Use of polyalkenyl succinimides-glycidol reaction products as antifoulants in hydrocarbon process media
US5336278A (en) 1993-05-13 1994-08-09 The Lubrizol Corporation Fuel composition containing an aromatic amide detergent
US5458793A (en) 1993-05-13 1995-10-17 The Lubrizol Corporation Compositions useful as additives for lubricants and liquid fuels
US5856524A (en) 1995-08-22 1999-01-05 The Lubrizol Corporation Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives
US6114547A (en) 1995-08-22 2000-09-05 The Lubrizol Corporation Hydroxy-substituted monolactones and use thereof as intermediates for preparing lubricating oil and fuel additives
US5739356A (en) 1995-08-22 1998-04-14 The Lubrizol Corporation Lactones useful as intermediates for preparing lubricating oil and fuel additives
US5777142A (en) 1995-08-22 1998-07-07 The Lubrizol Corporation Unsaturated hydroxycarboxylic compounds useful as intermediates for preparing lubricant and fuel additives
US5786490A (en) 1995-08-22 1998-07-28 The Lubrizol Corporation Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives
US6020500A (en) 1995-08-22 2000-02-01 The Lubrizol Corporation Hydroxy-substituted monolactones useful as intermediates for preparing lubricating oil and fuel additives
US5620949A (en) 1995-12-13 1997-04-15 The Lubrizol Corporation Condensation products of alkylphenols and aldehydes, and derivatives thereof
US5827805A (en) 1996-02-29 1998-10-27 The Lubrizol Corporation Condensates of alkyl phenols and glyoxal and products derived therefrom
US5885944A (en) 1996-05-21 1999-03-23 The Lubrizol Corporation Low chlorine polyalkylene substituted carboxylic acylating agent compositions and compounds derived therefrom
US6429178B1 (en) 1996-05-31 2002-08-06 Infineum Usa L.P. Calcium overbased metal-containing detergents
US6429179B1 (en) 1996-05-31 2002-08-06 Infineum U.S.A. L.P. Calcium overbased metal-containing detergents
US6281179B1 (en) 1996-05-31 2001-08-28 Infineum Usa L.P. Process for preparing an overbased metal-containing detergents
US6153565A (en) 1996-05-31 2000-11-28 Exxon Chemical Patents Inc Overbased metal-containing detergents
WO1998004656A1 (fr) 1996-07-31 1998-02-05 Elf Antar France Carburant pour moteurs diesel a faible teneur en soufre
US5840920A (en) 1996-08-08 1998-11-24 The Lubrizol Corporation Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives
US6207839B1 (en) 1996-08-08 2001-03-27 The Lubrizol Corporation Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives
US6147036A (en) 1996-08-08 2000-11-14 The Lubrizol Corporation Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives and derivatives thereof
US5688751A (en) 1996-08-14 1997-11-18 The Lubrizol Corporation Salicylate salts as lubricant additives for two-cycle engines
US6077909A (en) 1997-02-13 2000-06-20 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
US5912213A (en) 1997-06-05 1999-06-15 The Lubrizol Corporation Substituted carboxylic acylating agent compositions and derivatives thereof for use in lubricants and fuels
US5851966A (en) 1997-06-05 1998-12-22 The Lubrizol Corporation Reaction products of substituted carboxylic acylating agents and carboxylic reactants for use in fuels and lubricants
US6165235A (en) 1997-08-26 2000-12-26 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
US6001781A (en) 1997-09-10 1999-12-14 The Lubrizol Corporation Process for preparing condensation product of hydroxy-substituted aromatic compounds and glyoxylic reactants
US6107258A (en) 1997-10-15 2000-08-22 Ethyl Corporation Functionalized olefin copolymer additives
US6200936B1 (en) 1997-11-13 2001-03-13 The Lubrizol Corporation Salicyclic calixarenes and their use as lubricant additives
US6107257A (en) 1997-12-09 2000-08-22 Ethyl Corporation Highly grafted, multi-functional olefin copolymer VI modifiers
WO2000044857A2 (fr) 1998-12-11 2000-08-03 Infineum Usa Lp Materiaux macromoleculaires
US6683138B2 (en) 1999-09-16 2004-01-27 Texas Petrochemicals Lp Process for producing high vinylidene polyisobutylene
US6562913B1 (en) 1999-09-16 2003-05-13 Texas Petrochemicals Lp Process for producing high vinylidene polyisobutylene
US20050137363A1 (en) 1999-10-19 2005-06-23 Texas Peterochemicals Lp Process for producing mid-range vinylidene content polyisobutylene polymer products
US20060079652A1 (en) 1999-10-19 2006-04-13 Baxter C E Jr Mid-range vinylidene content polyisobutylene polymer product produced by liquid phase polymerization process
US6743266B2 (en) 2000-03-31 2004-06-01 Texaco, Inc. Fuel additive composition for improving delivery of friction modifier
US6559105B2 (en) 2000-04-03 2003-05-06 The Lubrizol Corporation Lubricant compositions containing ester-substituted hindered phenol antioxidants
US20040176552A1 (en) 2001-03-28 2004-09-09 Texas Petrochemicals Lp Process for producing mid-range vinylidene content polyisobutylene polymer products
US7037999B2 (en) 2001-03-28 2006-05-02 Texas Petrochemicals Lp Mid-range vinylidene content polyisobutylene polymer product and process for producing the same
US20050065045A1 (en) 2001-11-05 2005-03-24 Wilk Melody A. Sulfonate detergent system for improved fuel economy
US7407919B2 (en) 2001-11-05 2008-08-05 The Lubrizol Corporation Sulfonate detergent system for improved fuel economy
US7238650B2 (en) 2002-06-27 2007-07-03 The Lubrizol Corporation Low-chlorine, polyolefin-substituted, with amine reacted, alpha-beta unsaturated carboxylic compounds
WO2004035715A1 (fr) 2002-10-14 2004-04-29 Basf Aktiengesellschaft Utilisation d'homopolymères d'éther vinylique hydrocarbyle pour améliorer l'effet de promoteurs d'écoulement à froid
US7615521B2 (en) 2003-08-01 2009-11-10 The Lubrizol Corporation Mixed dispersants for lubricants
WO2005054314A2 (fr) 2003-12-04 2005-06-16 Basf Aktiengesellschaft Compositions d'huiles combustibles presentant de meilleures proprietes d'ecoulement a froid
US20050198894A1 (en) 2004-03-11 2005-09-15 Crompton Corporation Lubricant and fuel compositions containing hydroxy carboxylic acid and hydroxy polycarboxylic acid esters
US20060014651A1 (en) 2004-07-19 2006-01-19 Esche Carl K Jr Additives and lubricant formulations for improved antiwear properties
WO2006015130A1 (fr) 2004-07-30 2006-02-09 The Lubrizol Corporation Modifiants de viscosité de dispersant contenant des amines aromatiques
US7790661B2 (en) 2004-07-30 2010-09-07 The Lubrizol Corporation Dispersant viscosity modifiers containing aromatic amines
WO2006044411A1 (fr) 2004-10-12 2006-04-27 The Lubrizol Corporation Dérivés d’acide tartarique permettant d’augmenter les économies de combustible et jouant le rôle d’agents anti-usure dans les huiles de carter, et préparations basées sur lesdits dérivés
US20090054278A1 (en) 2005-02-18 2009-02-26 The Lubrizol Corporation Multifunctional Dispersants
US7727943B2 (en) 2005-03-28 2010-06-01 The Lubrizol Corporation Titanium compounds and complexes as additives in lubricants
US7951211B2 (en) 2005-06-16 2011-05-31 The Lubrizol Corporation Quaternary ammonium salt detergents for use in fuels
US8083814B2 (en) 2006-09-01 2011-12-27 The Lubrizol Corporation Quaternary ammonium salt of a mannich compound
US20080113890A1 (en) 2006-11-09 2008-05-15 The Lubrizol Corporation Quaternary Ammonium Salt of a Polyalkene-Substituted Amine Compound
US20080119378A1 (en) 2006-11-21 2008-05-22 Chevron Oronite Company Llc Functional fluids comprising alkyl toluene sulfonates
WO2008147704A1 (fr) 2007-05-24 2008-12-04 The Lubrizol Corporation Composition lubrifiante contenant un agent anti-usure
US20120255512A1 (en) 2008-05-13 2012-10-11 Afton Chemical Corporation Fuel additives for treating internal deposits of fuel injectors
WO2010014655A1 (fr) 2008-07-31 2010-02-04 The Lubrizol Corporation Nouveaux copolymères, et compositions lubrifiantes de ceux-ci
US20110219674A1 (en) 2008-10-10 2011-09-15 The Lubrizol Corporation Additives to Reduce Metal Pick-Up in Fuels
US8404625B2 (en) 2009-08-18 2013-03-26 The Lubrizol Corporation Lubricating composition containing an antiwear agent
US8557755B2 (en) 2009-08-18 2013-10-15 The Lubrizol Corporation Lubricating composition containing an antiwear agent
US8530395B1 (en) 2009-08-18 2013-09-10 The Lubrizol Corporation Lubricating composition containing an antiwear agent
WO2011022317A1 (fr) 2009-08-18 2011-02-24 The Lubrizol Corporation Composition lubrifiante contenant un agent anti-usure
WO2011095819A1 (fr) 2010-02-05 2011-08-11 Innospec Limited Compositions de carburant
WO2011110860A1 (fr) 2010-03-10 2011-09-15 Innospec Limited Composition de carburant comprenant un additif détergent et un additif sel d'ammonium quaternaire
US20110258917A1 (en) 2010-04-27 2011-10-27 Basf Se Quaternized terpolymer
WO2011141731A1 (fr) 2010-05-10 2011-11-17 Innospec Limited Composition, procédé et utilisation
US20110315107A1 (en) 2010-06-25 2011-12-29 Basf Se Quaternized copolymer
WO2012004300A1 (fr) * 2010-07-06 2012-01-12 Basf Se Composés azotés quaternisés exempts d'acide et utilisation desdits composés comme additifs pour carburants ou pour lubrifiants
US20120010112A1 (en) 2010-07-06 2012-01-12 Basf Se Acid-free quaternized nitrogen compounds and use thereof as additives in fuels and lubricants
US20120149617A1 (en) 2010-12-09 2012-06-14 Basf Se Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines and use thereof as a fuel additive or lubricant additive
US20130133243A1 (en) 2011-06-28 2013-05-30 Basf Se Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants
WO2013017884A1 (fr) 2011-08-03 2013-02-07 Innospec Limited Compositions de carburant
WO2013017886A1 (fr) 2011-08-03 2013-02-07 Innospec Limited Compositions de carburant
WO2013017889A1 (fr) 2011-08-03 2013-02-07 Innospec Limited Compositions de carburant
US20130074794A1 (en) 2011-09-22 2013-03-28 Afton Chemical Corporation Fuel additives for treating internal deposits of fuel injectors
US20130225463A1 (en) 2011-11-04 2013-08-29 Markus Hansch Quaternized polyether amines and their use as additive for fuels and lubricants
WO2013070503A1 (fr) 2011-11-11 2013-05-16 Afton Chemical Corporation Additif pour carburant pour un meilleur rendement des moteurs à injection directe du carburant
US20130118062A1 (en) 2011-11-11 2013-05-16 Afton Chemical Corporation Fuel additive for improved performance of direct fuel injected engines
US20130312318A1 (en) * 2012-05-25 2013-11-28 Basf Se Use of a reaction product of carboxylic acids with aliphatic polyamines for improving or boosting the separation of water from fuel oils
US20130333649A1 (en) 2012-06-13 2013-12-19 Afton Chemical Corporation Fuel additive for improved performance in fuel injected engines
WO2014007379A1 (fr) * 2012-07-05 2014-01-09 Ｊｘ日鉱日石エネルギー株式会社 Composé succinimide, additif pour huile lubrifiante et composition d'huile lubrifiante

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Chemistry and Technology of Lubricants", 2010, pages: 219
"Maleic Anhydride", 1982, PLENUM PRESS, pages: 147 - 149
"Ullmann's Encyclopedia of Industrial Chemistry", article "Amines, aliphatic"
N. A. PLATE; V. P. SHIBAEV: "Comb-Like Polymers. Structure and Properties", J. POLY. SCI. MACROMOLECULAR REVS., vol. 8, 1974, pages 117 - 253, XP009033606, DOI: doi:10.1002/pol.1974.230080103

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EP3536766B1 (fr) 2020-12-09
EP3149130B1 (fr) 2019-04-03
WO2015184276A1 (fr) 2015-12-03
CN106661473A (zh) 2017-05-10
US20170107441A1 (en) 2017-04-20
BR112016028080B1 (pt) 2022-06-14
DK3149130T3 (da) 2019-05-20
EP3536766A8 (fr) 2020-02-26
BR112016028080A2 (pt) 2020-12-15
EP3149130A1 (fr) 2017-04-05
SG11201609882UA (en) 2016-12-29

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