EP3536766B1

EP3536766B1 - Epoxide quaternized quaternary ammonium salts

Info

Publication number: EP3536766B1
Application number: EP19166380.6A
Authority: EP
Inventors: Paul E. Adams; James H. Bush; Hannah Greenfield; Paul R. STEVENSON; David J. Moreton
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2014-05-30
Filing date: 2015-05-29
Publication date: 2020-12-09
Anticipated expiration: 2035-05-29
Also published as: EP3536766A1; EP3149130B1; WO2015184276A1; CN106661473A; US20170107441A1; BR112016028080B1; DK3149130T3; EP3536766A8; BR112016028080A2; EP3149130A1; SG11201609882UA

Description

FIELD OF THE INVENTION

The present technology is related to quaternary ammonium salts prepared with alcohol functionalized 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.

BACKGROUND OF THE INVENTION

Deposit formation in diesel fuel injector nozzles is highly problematic, resulting in incomplete diesel combustion, and therefore power loss and misfiring. Traditionally, polyisobutylene succinimide detergents have been used to inhibit injector fouling, but these materials have shown poor efficacy in modern engines. A new class of compounds based on quaternized polyisobutylene succinimides has been shown to provide improved detergency performance in both the traditional and modern diesel engines.
Although deposit control is the main function required of detergent molecules, there are a number of additional performance attributes which are desired. One of these is the ability of the detergent to shed water, or resolve water in oil emulsions. The entrainment of water in, for example, crude oil or downstream fuel pipelines, and during product transfer, can result in the formation of stable emulsions and suspended matter in the crude or fuel. Such emulsions can plug filters or otherwise make such emulsion containing fuels unacceptable. This could also result in corrosion issues downstream.
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 EP 0 183 478 A2 discloses glycidol modified succinimides.

SUMMARY OF THE INVENTION

The present technology provides a composition comprising an epoxide quat prepared with alcohol functionalized epoxides. The epoxide quat itself is the reaction product of (a) a quaternizable compound and (b) a quaternizing agent comprising alcohol functionalized epoxides.
The quaternizable compound is 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 has a number average molecular weight (M_n) of from 100 to 5000 as measured using gel permeation chromatography (GPC) based on a polystyrene calibration standard.
In an embodiment, the quaternizable amino group can be a primary, secondary or tertiary amino group. The hydrocarbyl-substituted acylating agent is polyisobutenyl succinic anhydride or polyisobutenyl succinic acid.
In some embodiments, 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.
In an embodiment, 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.
In another embodiment, 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 some embodiments, 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.
In some embodiments, the compositions described above can further include at least one other additive. In some instances, the at least one other additive can be a detergent, a demulsifier, or a mixture thereof. In some instances the at least one other additive can be at least one hydrocarbyl-substituted succinic acid. In some instances, the at least one other additive can be at least one hydrocarbyl-substituted quaternary ammonium salt. In some instances where the at least one other additive is a non-quaternized or quaternized hydrocarbyl-substituted succinic acid, the hydrocarbyl-substituent can be a polyisobutylene having a number average molecular weight (M_n) of from about 100 to about 5000. In an embodiment, 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 an oil of lubricating viscosity.
A still further aspect of the present technology provides a method of operating an internal combustion engine.
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.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the demulsification test results of a reference embodiment of the disclosed technology.
FIG. 2 shows the CEC F-23-01 XUD-9 test results at 10 ppm of a reference embodiment of the disclosed technology.
FIG. 3 shows the CEC F-23-01 XUD-9 test results at 30 ppm of a reference embodiment of the disclosed technology.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below by way of non-limiting illustration.
One aspect of the current technology relates to a composition of an imide containing quaternary ammonium salt. The quaternary ammonium salt (herein referred to as "epoxide quats") may be prepared with alcohol functionalized epoxides.

Epoxide Quats

The production of a quaternary ammonium salt generally results in a mixture of compounds including a quaternary ammonium salt or salts, and this mixture may be difficult to define apart from the process steps employed to produce the quaternary ammonium salt. Further, the process by which a quaternary ammonium salt is produced can be influential in imparting distinctive structural characteristics to the final quaternary ammonium salt product that can affect the properties of the quaternary ammonium salt product. Thus, in one embodiment, the epoxide quats of the present technology may be described as a reaction product of (a) a quaternizable compound, and (b) a quaternizing agent. As used herein, reference to epoxide quat(s) includes references to the mixture compounds including a quaternary ammonium salt or salts prepared with alcohol functionalized epoxides, as well as referring to the quaternary ammonium salt itself.
The quaternizable compound of (a) employed to prepare the epoxide quat may itself be the reaction product of (i) a hydrocarbyl-substituted acylating agent, and (ii) a nitrogen containing compound. The hydrocarbyl-substituted acylating agent of (a)(i) can be an acylating agent functionalized with a hydrocarbyl-substituent having a number average molecular weight of 100 to 5000.
The number average molecular weight of the materials described herein is measured using gas permeation chromatography (GPC) using a Waters GPC 2000 equipped with a refractive index detector and Waters Empower™ data acquisition and analysis software. The columns are polystyrene (PLgel, 5 micron, available from Agilent/Polymer Laboratories, Inc.). For the mobile phase, individual samples are dissolved in tetrahydrofuran and filtered with PTFE filters before they are injected into the GPC port.

Waters GPC 2000 Operating Conditions:

Injector, Column, and Pump/Solvent compartment temperatures: 40° C

Autosampler Control: Run time: 40 minutes
Injection volume: 300 microliter
Pump: System pressure: ∼90 bars (Max. pressure limit: 270 bars, Min. pressure limit: 0 psi)
Flow rate: 1.0 ml/minute
Differential Refractometer (RI): Sensitivity: -16; Scale factor: 6

Examples of quaternary ammonium salts and methods for preparing the same are described in the following patents, which are hereby incorporated by reference, US 4,253,980 , US 3,778,371 , US 4,171,959 , US 4,326,973 , US 4,338,206 , US 5,254,138 , and US 7,951,211 .
Details regarding the quaternizable compound, and specifically, the hydrocarbyl-substituted acylating agent and the nitrogen containing compound, as well as the quaternizing agent, are provided below.

The Hydrocarbyl Substituted Acylating Agent

The hydrocarbyl substituted acylating agent employed to prepare the quaternizable compound can be the reaction product of the precursor to the hydrocarbyl-substituent, which is a long chain hydrocarbon, generally a polyolefin, with a monounsaturated carboxylic acid reactant such as maleic acid.
The hydrocarbyl-substituent is a long chain hydrocarbyl group. In one embodiment, the hydrocarbyl group can have a number average molecular weight (M_n) of from about 100 or 300 to about 5000, or from about 500 to about 2500. The Mn of the hydrocarbyl group can also be from about 1300 to about 3000. The M_n of the hydrocarbyl-substituent can also be from 1500 to 2800 or 2900, or from 1700 to 2700, or from 1900 to 2600, or 2000 to 2500. In an embodiment, the M_n can be from about 300 to about 750. The M_n of the hydrocarbyl-substituent can also be from about 350 to 700, and in some cases from 400 to 600, or 650. In yet other embodiments the M_n of the hydrocarbyl-substituent can also be 550, or 1000, or 2300. In yet another embodiment, the hydrocarbyl-substituent may have a number average molecular weight of 1000 to 2300.
Olefin polymers for reaction with the monounsaturated carboxylic acids include isobutylene, The polymers are polyisobutylene.
In other embodiments, the hydrocarbyl-substituted acylating agent may be a "conventional" vinylidene polyisobutylene (PIB) wherein less than 20% of the head groups are vinylidene head groups as measured by nuclear magnetic resonance (NMR). Alternatively, the hydrocarbyl-substituted acylating agent may be a mid-vinylidene PIB or a high-vinylidene PIB. In mid-vinylidene PIBs, the percentage of head groups that are vinylidene groups can range from greater than 20% to 70%. In high-vinylidene PIBs, the percentage of head groups that are vinylidene head groups is greater than 70%.
Methods of making hydrocarbyl substituted acylating agents from the reaction of the monounsaturated carboxylic acid reactant and the compound of formula (I) are well known in the art and disclosed in the following patents: U.S. Pat. Nos. 3,361,673 and 3,401,118 to cause a thermal "ene" reaction to take place; U.S. Pat. Nos. 3,087,436 ; 3,172,892 ; 3,272,746 , 3,215,707 ; 3,231,587 ; 3,912,764 ; 4,110,349 ; 4,234,435 ; 6,077,909 ; 6,165,235 .

Nitrogen Containing Compound

The 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.
In one embodiment, the nitrogen containing compound can be represented by the following formulas:
wherein X is an alkylene group containing 1 to 4 carbon atoms; R₂ may be a H or a hydrocarbyl group; and R₃ and R₄ are hydrocarbyl groups.
wherein X is a alkylene group containing about 1 to about 4 carbon atoms; R3 and R4 are hydrocarbyl groups.
Examples of the 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. 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-1-propanol, 3-diethylamino-1-propanol, 1-dimethylamino-2-propanol, 1-diethylamino-2-propanol, 2-dimethylamino-2-methyl-1-1propanol, 5-dimethylamino-2-propanol, 2-[2-(dimethylamino)ethoxy]-ethanol, 4-methyl-2-(piperidino methyl)phenol, 1-benzyl-3-pyrrolidinol, 1-benzylpyrrolidine-2-methanol, 2,4,6-tri(dimethylaminomethyl)phenol, dialkoxylated amines such as Ethermeen T12. In some embodiments, the nitrogen containing compound excludes dimethylaminopropylamine.
In one embodiment, 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
In one embodiment, the nitrogen containing compound can be represented by at least one of formulas X or XI:
wherein each X can be, individually, a C1 to C6 hydrocarbylene group, and each R can be, individually, a hydrogen or a C1 to C6 hydrocarbyl group. In one embodiment, X can be, for example, a C1, C2 or C3 alkylene group. In the same or different embodiments, each R can be, for example, H or a C1, C2 or C3 alkyl group.

Quaternizable Compound

The hydrocarbyl substituted acylating agents and nitrogen containing compounds described above are reacted together to form a quaternizable compound. Methods and process for reacting the hydrocarbyl substituted acylating agents and nitrogen containing compounds are well known in the art.
In embodiments, 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. In yet another embodiments 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. At the foregoing temperatures water may be produced during the condensation, which is referred to herein as the water of reaction. In some embodiments, 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 hydrocarbyl substituted acylating agents and nitrogen containing compounds may be reacted at a ratio of 1:1, but the reaction may also contain the respective reactants (i.e., hydrocarbyl substituted acylating agent:nitrogen containing compound) in ratios from 3:1 to 1:1.2, or from 2.5:1 to 1:1.1, and in some embodiments from 2:1 to 1:1.05.

Quaternizing agent

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 include, alcohol functionalized epoxides.
Exemplary epoxides, can be represented by the following formula:
where R¹, R², R³ and R⁴ can be independently H, a C₄ to C₁₄ hydrocarbyl group, or an alcohol containing hydrocarbyl group. 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.
Exemplary alcohol functionalized epoxides can include those of formula VIII where R¹, R², R³ and R⁴ can be independently H or a hydroxyl containing hydrocarbyl group. In an embodiment, hydroxyl containing hydrocarbyl group can contain from 2 to 32, or from 3 to 28, or even from 3 to 24 carbon atoms. Exemplary alcohol functionalized epoxide derivatives can include for example, glycidol and the like.
In some embodiments 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. In other embodiments, 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.
In certain embodiments 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.
In some embodiments, the quaternizing agent can be employed in the presence of a protic solvent, such as, for example, 2-ethylhexanol, water, and combinations thereof. In some embodiments, the quaternizing agent can be employed in the presence of an acid. In yet another embodiment, the quaternizing agent can be employed in the presence of an acid and a protic solvent. In some embodiments, the acid can be an acid component in addition to the acid group present in the structure of the acylating agent. In further embodiments the reaction can be free of, or essentially free of, any additional acid component other than the acid group present in the structure of the acylating agent. By "free of' it is meant completely free, and by "essentially free" it is meant an amount that not materially affect the essential or basic and novel characteristics of the composition, such as, for example, less than 1% by weight.

Structure

While the process to prepare the epoxide quats can produce a mixture that is not readily definable apart from the process steps, certain structural components may be expected in some circumstances.
In some embodiments the epoxide quats can comprise, consist essentially of, or consist of a cation represented by the following formula:
wherein: R²¹ is a hydrocarbyl group containing from 1 to 10 carbon atoms; R²² is a hydrocarbyl group containing from 1 to 10 carbon atoms; R²³ is a hydrocarbylene group containing from 1 to 20 carbon atoms; R²⁴ 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. In some embodiments, R²⁴ 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.
In some embodiments the epoxide quats can comprise, consist essentially of, or consist of a cation represented by the following formula:
wherein: R²¹ and R²² are hydrocarbyl groups containing from 1 to 10 carbon atoms; R²³ is a hydrocarbylene group containing from 1 to 20 carbon atoms; R²⁴ 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 is a group derived from the quaternizing agent; and Y is oxygen or nitrogen. In some embodiments, R²⁴ 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.
In some embodiments the epoxide quats can comprise, consist essentially of, or consist of a cation represented by the following formulas:
or
wherein: R can be a C₁ to C₆ alkyl group; R₁ and R₂, individually, can be a C₁ to C₆ hydrocarbyl group, for example a C₁, C₂, or C₃ alkyl group; R₃, R₄, R₅ and R₆, individually, can be hydrogen or a C₁ to C₆ hydrocarbyl group, such as, for example, a C₁, C₂, or C₃ alkyl group; R²⁴ 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; X₁ and X₂, individually, can be H or a group derived from the quaternizing agent, so long as at least one of X₁ and X₂ is a group derived from the quaternizing agent. In some embodiments, R²⁴ 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.
In some embodiments the epoxide quats can comprise, consist essentially of, or consist of a cation represented by the following formula:
wherein: R²³ is a hydrocarbylene group containing from 1 to 20 carbon atoms; R²⁴ 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. In some embodiments, R²⁴ 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

In one embodiment, the present technology provides a composition comprising an epoxide quat, and the use of the composition in a lubricating composition with an oil of lubricating viscosity.

Oil of Lubricating Viscosity

In lubricating composition embodiments, the compositions of the present invention can comprise an oil of lubricating viscosity. Such oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof. A more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704 , paragraphs [0054] to [0056]. A more detailed description of natural and synthetic lubricating oils is provided in paragraphs [0058] to [0059] respectively of WO2008/147704 . Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to liquid synthetic procedure as well as other gas-to-liquid oils.
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.

Miscellaneous

The 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.
Although 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). The materials described in the following U.S. Patents are illustrative: U.S. Pat. Nos. 3,036,003 ; 3,236,770 ; 3,414,347 ; 3,448,047 ; 3,461,172 ; 3,539,633 ; 3,586,629 ; 3,591,598 ; 3,634,515 ; 3,725,480 ; 3,726,882 ; and 3,980,569 . Other suitable 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. 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. Other 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. Combustion improvers include for example octane and cetane improvers. Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
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 α-hydroxy acid with an amine and/or alcohol optionally in the presence of a known esterification catalyst. Examples of α-hydroxy acids include glycolic acid, lactic acid, α-hydroxy dicarboxylic acid (such as tartaric acid) and/or an α-hydroxy tricarboxylic acid (such as citric acid), with an amine and/or alcohol, optionally in the presence of a known esterification catalyst. These 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. Examples of 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. In an embodiment, 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. In some embodiments, the detergent may be a C₆ to C₁₈ substituted succinic acid, amide or ester. A more thorough description of the hydrocarbyl substituted acylating agent detergents can be found from paragraph [0017] to [0036] of U.S. Publication 2011/0219674, published September 15, 2011 .
In one embodiment, 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.
In an embodiment, 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. In an embodiment, 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.
In yet another embodiment 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, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.
In an embodiment the nitrogen containing compound of the additional quaternary ammonium salts is an imidazole or nitrogen containing compound of either of formulas.
wherein R may be a C₁ to C₆ alkylene group; each of R₁ and R₂, individually, may be a C₁ to C₆ hydrocarbylene group; and each of R₃, R₄, R₅, and R₆, individually, may be a hydrogen or a C₁ to C₆ hydrocarbyl group.
In other embodiments, 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. In some cases the quaternizing agent can be a hydrocarbyl epoxide. In some cases the quaternizing agent can be a hydrocarbyl epoxide in combination with an acid. In some cases the quaternizing agent can be a salicylate, oxalate or terephthalate. In an embodiment the hydrocarbyl epoxide is an alcohol functionalized epoxides or C₄ to C₁₄ epoxides.
In some embodiments, 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 R⁰, R¹, R² and R³ 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. 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.
Such conventional overbased materials and their methods of preparation are well known to those skilled in the art. 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 . In certain embodiments, 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 (also sometimes referred to as viscosity index improvers or viscosity modifiers) 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 (DVM) 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. In certain embodiments 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. Often the antiwear agent is a zinc dialkyldithiophosphate (ZDP). For a typical ZDP, which may contain 11 percent P (calculated on an oil free basis), suitable amounts may include 0.09 to 0.82 percent by weight. Non-phosphorus-containing anti-wear agents include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins. In some embodiments 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 C₅ - C₁₇ 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.
Seal swell agents include sulpholene derivatives Exxon Necton-37™ (FN 1380) and Exxon Mineral Seal Oil™ (FN 3200).

Engine Oil Lubricants

In different embodiments the technology provides engine oil lubricating compositions that can be employed in internal combustion engines. The internal combustion engine may be spark ignition or compression ignition. The internal combustion engine may be a 2-stroke or 4-stroke engine. The internal combustion engine may be a passenger car engine, a light duty diesel engine, a heavy duty diesel engine, a motorcycle engine, or a 2-stroke or 4-stroke marine diesel engine. Typically the internal combustion engine may be a passenger car engine, or a heavy duty diesel internal combustion engine.
In one embodiment an engine oil lubricant composition of the invention comprises in addition to the quaternary ammonium salts of the present technology an overbased metal-containing detergent, or mixtures thereof.
Overbased detergents are known in the art. Overbased materials, otherwise referred to as overbased or superbased salts, are generally single phase, homogeneous 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 prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, typically carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter such as a calcium chloride, acetic acid, phenol or alcohol. The acidic organic material will normally have a sufficient number of carbon atoms to provide a degree of solubility in oil. The amount of "excess" metal (stoichiometrically) is commonly expressed in terms of metal ratio. The term "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. The term "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. In one embodiment 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. In one embodiment the sulfonate detergent may be a metal salt of one or more oil-soluble alkyl toluene sulfonate compounds as disclosed in paragraphs [0046] to [0053] of US Patent Application 2008/0119378 .
In one embodiment 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 . Where, for example, a hybrid sulfonate/phenate detergent is employed, the hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
The other detergent may have an alkali metal, an alkaline earth metal, or zinc counterion. In one embodiment the metal may be sodium, calcium, barium, or magnesium. Typically other detergent may be sodium, calcium, or magnesium containing detergent (typically, calcium, or magnesium containing detergent).
The other detergent may typically be an overbased detergent of sodium, calcium or magnesium salt of the phenates, sulfur-containing phenates, salixarates and salicylates. Overbased phenates and salicylates typically have a total base number of 180 to 450 TBN (on an oil free basis).
Phenate detergents are typically derived from p-hydrocarbyl phenols. Alkylphenols of this type may be coupled with sulfur and overbased, coupled with aldehyde and overbased, or carboxylated to form salicylate detergents. Suitable alkylphenols include those alkylated with oligomers of propylene, i.e. tetrapropenylphenol (i.e. p-dodecylphenol or PDDP) and pentapropenylphenol. Other suitable alkylphenols include those alkylated with alpha-olefins, isomerized alpha-olefins, and polyolefins like polyisobutylene. In one embodiment, 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 overbased detergent may be present at 0 wt % to 10 wt %, or 0.1 wt % to 10 wt %, or 0.2 wt % to 8 wt %, or 0.2 wt % to 3 wt %. For example in a heavy duty diesel engine the detergent may be present at 2 wt % to 3 wt % of the lubricant composition. For a passenger car engine the detergent may be present at 0.2 wt % to 1 wt % of the lubricant composition. In one embodiment, an engine oil lubricant composition comprises at least one overbased detergent with a metal ratio of at least 3, or at least 8, or at least 15.
In an embodiment an engine oil lubricant composition comprising the epoxide quats of the present technology may further include a dispersant, or mixtures thereof. The dispersant may be chosen from a succinimide dispersant, a Mannich dispersant, a succinamide dispersant, a polyolefin succinic acid ester, amide, or ester-amide, or mixtures thereof.
In one embodiment an engine oil lubricant composition includes a dispersant or mixtures thereof. The dispersant may be present as a single dispersant. The dispersant may be present as a mixture of two or more (typically two or three) different dispersants, wherein at least one may be a succinimide dispersant.
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. In one embodiment the aliphatic polyamine may be ethylenepolyamine. In one embodiment the aliphatic polyamine may be chosen from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
In one embodiment the dispersant may be a polyolefin succinic acid ester, amide, or ester-amide. For instance, a polyolefin succinic acid ester may be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof. A polyolefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and an amine (such as a diamine, typically diethyleneamine).
The dispersant may be an N-substituted long chain alkenyl succinimide. An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide. Typically the polyisobutylene from which polyisobutylene succinic anhydride may be derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500. Succinimide dispersants and their preparation are disclosed, for instance in US Patents 3,172,892 , 3,219,666 , 3,316,177 , 3,340,281 , 3,351,552 , 3,381,022 , 3,433,744 , 3,444,170 , 3,467,668 , 3,501,405 , 3,542,680 , 3,576,743 , 3,632,511 , 4,234,435 , Re 26,433 , and 6,165,235 , 7,238,650 and EP Patent Application 0 355 895 A .
The dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron compounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. In one embodiment the post-treated dispersant is borated. In one embodiment the post-treated dispersant may be reacted with dimercaptothiadiazoles. In one embodiment the post-treated dispersant may be reacted with phosphoric or phosphorous acid. In one embodiment the post-treated dispersant may be reacted with terephthalic acid and boric acid (as described in US Patent Application US2009/0054278 .
In one embodiment the dispersant may be borated or non-borated. Typically a borated dispersant may be a succinimide dispersant. In one embodiment, 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. In one embodiment, 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 be prepared/obtained/obtainable from reaction of succinic anhydride by an "ene" or "thermal" reaction, by what may be referred to as a "direct alkylation process." The "ene" reaction mechanism and general reaction conditions are summarized in "Maleic Anhydride", pages, 147-149, Edited by B.C. Trivedi and B.C. Culbertson and Published by Plenum Press in 1982. The dispersant prepared by a process that includes an "ene" reaction may be a polyisobutylene succinimide having a carbocyclic ring present on less than 50 mole %, or 0 to less than 30 mole %, or 0 to less than 20 mole %, or 0 mole % of the dispersant molecules. The "ene" reaction may have a reaction temperature of 180 °C to less than 300 °C, or 200 °C to 250 °C, or 200 °C to 220 °C.
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. In one embodiment 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.
In one embodiment the dispersant may be a succinimide dispersant may comprise a polyisobutylene succinimide, wherein the polyisobutylene from which polyisobutylene succinimide is derived has a number average molecular weight of 350 to 5000, or 750 to 2500.
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.
In one embodiment an engine oil lubricant composition comprising the epoxide quats of the present technology may be a lubricant composition further comprising a molybdenum compound. The molybdenum compound may be an antiwear agent or an antioxidant. The molybdenum compound may be chosen from molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof. The molybdenum compound may provide the lubricant composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
In another embodiment an engine oil lubricant composition comprising the epoxide quats of the present technology may further comprise an antioxidant. Antioxidants include sulfurized olefins, diarylamines, alkylated diarylamines, hindered phenols, molybdenum compounds (such as molybdenum dithiocarbamates), hydroxyl thioethers, or mixtures thereof. In one embodiment the lubricant composition includes an antioxidant, or mixtures thereof. The antioxidant may be present at 0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt %, or 0.5 wt % to 3 wt %, or 0.3 wt % to 1.5 wt % of the lubricant composition.
In one embodiment an engine oil lubricant composition comprising the epoxide quats of the present technology further comprises a phenolic or an aminic antioxidant or mixtures thereof, and wherein the antioxidant is present at 0.1 wt % to 3 wt %, or 0.5 wt % to 2.75 wt %, or 1 wt % to 2.5 wt %.
The diarylamine or alkylated diarylamine may be a phenyl-α-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. In one embodiment the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In one embodiment 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.
The hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group. The phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group. Examples of suitable hindered phenol antioxidants 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. In one embodiment the hindered phenol antioxidant may be an ester and may include, e.g., Irganox™ L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105 .
Examples of 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-Lube™ S-100, S-165, S-600 and 525, or mixtures thereof.
In one embodiment 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 include a block copolymer comprising (i) a vinyl aromatic monomer block and (ii), a conjugated diene olefin monomer block (such as a hydrogenated styrene-butadiene copolymer or a hydrogenated styrene-isoprene copolymer), a polymethacrylate, an ethylene-alpha olefin copolymer, a hydrogenated star polymer comprising conjugated diene monomers such as butadiene or isoprene, or a star polymer of polymethacrylate, or mixtures thereof.
In an embodiment 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.
In one embodiment the dispersant viscosity modifier comprises an olefin copolymer further functionalized with a dispersant amine group. Typically, the olefin copolymer is an ethylene-propylene copolymer. The olefin copolymer has a number average molecular weight of 5000 to 20,000, or 6000 to 18,000, or 7000 to 15,000. The olefin copolymer may have a shear stability index of 0 to 20, or 0 to 10, or 0 to 5 as measured by the Orbahn shear test (ASTM D6278) as described above.
The formation of a dispersant viscosity modifier is well known in the art. The dispersant viscosity modifier may include for instance those described in U.S. Patent US 7,790,661 column 2, line 48 to column 10, line 38.
In one embodiment 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 α-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).
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; polymethacrylates functionalized with an amine, or styrene-maleic anhydride copolymers reacted with an amine. Suitable amines may be aliphatic or aromatic amines and polyamines. Examples of suitable aromatic amines include nitroaniline, aminodiphenylamine (ADPA), hydrocarbylene coupled polyaromatic amines, and mixtures thereof. More detailed description of dispersant viscosity modifiers are disclosed in International Publication WO2006/015130 or U.S. Patents 4,863,623 ; 6,107,257 ; 6,107,258 ; 6,117,825 ; and US 7,790,661 .
In one embodiment 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]). In one embodiment 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.
In one embodiment an engine oil lubricant composition comprising the epoxide quats disclosed herein further comprises a dispersant viscosity modifier. The dispersant viscosity modifier may be present at 0 wt % to 5 wt %, or 0 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.2 wt % to 1.2 wt % of the lubricant composition.
In one embodiment an engine oil lubricant composition comprising the epoxide quats of the present technology further includes a friction modifier. In one embodiment 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. As used herein the term "fatty alkyl" or "fatty" in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.
Examples of 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; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or reaction products from fatty carboxylic acids with guanidine, aminoguanidine, urea, or thiourea and salts thereof.
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.
In one embodiment the friction modifier may be a long chain fatty acid ester. In another embodiment 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. Examples of 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 .
Another class of additives includes 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. In one embodiment 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. In one embodiment, the titanium alkoxide is titanium (IV) isopropoxide. In one embodiment, the titanium alkoxide is titanium (IV) 2-ethylhexoxide. In one embodiment, the titanium compound comprises the alkoxide of a vicinal 1,2-diol or polyol. In one embodiment, the 1,2-vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty acid is oleic acid.
In one embodiment, the oil soluble titanium compound is a titanium carboxylate. In one embodiment 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. Typically the phosphorus-containing antiwear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium phosphate salts, or mixtures thereof.
In one embodiment 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.
In one embodiment, an engine oil lubricant composition further comprises one or more zinc dialkyldithiophosphate such that the amine (thio)phosphate additive of the invention provides at least 50% of the total phosphorus present in the lubricating composition, or at least 70% of the total phosphorus, or at least 90% of the total phosphorus in the lubricating composition. In one embodiment, the lubricant composition is free or substantially free of a zinc dialkyldithiophosphate.
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.
In one embodiment 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 represented by Formula:
wherein

Y and Y' are independently -O-, >NH, >NR3, or an imide group formed by taking together both Y and Y' groups and forming a R¹-N< group between two >C=O groups;
X is independently -Z-O-Z'-, >CH₂, >CHR⁴, >CR⁴R⁵, >C(OH)(CO₂R²), >C(CO₂R²)₂, or >CHOR⁶;
Z and Z' are independently >CH₂, >CHR⁴, >CR⁴R⁵, >C(OH)(CO₂R²), or >CHOR⁶;
n is 0 to 10, with the proviso that when n=1, X is not >CH₂, and when n=2, both X's are not >CH₂;
m is 0 or 1;
R¹ is independently hydrogen or a hydrocarbyl group, typically containing 1 to 150 carbon atoms, with the proviso that when R¹ is hydrogen, m is 0, and n is more than or equal to 1;
R² is a hydrocarbyl group, typically containing 1 to 150 carbon atoms;
R³, R⁴ and R⁵ are independently hydrocarbyl groups; and
R⁶ is hydrogen or a hydrocarbyl group, typically containing 1 to 150 carbon atoms.

In one embodiment 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. For example the compound may be represented by formulae:
or
or
wherein

Y is independently oxygen or >NH or >NR¹;
R¹ is independently a hydrocarbyl group, typically containing 4 to 30, or 6 to 20, or 8 to 18 carbon atoms;
Z is hydrogen or methyl;
Q is the residue of a diol, triol or higher polyol, a diamine, triamine, or higher polyamine, or an aminoalcohol (typically Q is a diol, diamine or aminoalcohol)
g is 2 to 6, or 2 to 3, or 2;
q is 1 to 4, or 1 to 3 or 1 to 2;
n is 0 to 10, 0 to 6, 0 to 5, 1 to 4, or 1 to 3; and
Ak¹ is an alkylene group containing 1 to 5, or 2 to 4 or 2 to 3 (typically ethylene) carbon atoms; and
b is 1 to 10, or 2 to 8, or 4 to 6, or 4.

The compound is known and is described in International publication WO 2011/022317 , and also in granted US Patents 8,404,625 , 8,530,395 , and 8,557,755 .

Industrial Application

In one embodiment the invention is useful in 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.
In one embodiment, 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. Accordingly, in another embodiment, 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. In 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. In yet another embodiment, the unit direct injection or common rail systems may further comprise an optional turbocharged or supercharged direct injection system.
In a further embodiment, the imide quat technology is useful for providing at least equivalent, if not improved detergency (deposit reduction and/or prevention) performance in both the traditional and modern diesel engine compared to a 1000 M_n quaternary ammonium compound. In addition, the technology can provide improved water shedding (or demulsifying) performance compared to 1000 M_n quaternary ammonium compounds in both the traditional and modern diesel engine. In yet another embodiment, the disclosed technology may be used to improve the cold temperature operability or performance of a diesel fuel (as measured by the ARAL test).
In yet another embodiment, the lubricating composition comprising an epoxide quat is useful for lubricating an internal combustion engine (for crankcase lubrication).
Embodiments of the present technology may provide 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.
As used herein, the term "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. Examples of 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, contain other than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. In general, 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.
It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by admixing the components described above.

EXAMPLES

The invention will be further illustrated by the following examples, which sets forth particularly advantageous embodiments. While the examples are provided to illustrate the present invention, they are not intended to limit it.

Example 1 - Formation of 1000 M _n Polyisobutylene Succinic Anhydride (PIBSA)

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 Eurotherm™ temperature controller (reaction kit).
Maleic anhydride (245 g, 2.5 moles) is then charged to the reaction vessel. The batch is agitated under a nitrogen blanket and slowly heated to 203 °C over a 90 minute period. The batch is maintained at 203°C for 24 hours.
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.

Example 2 - Formation of Ouaternizable Compound - 1000 M _n PIBSA and Dimethylaminopropylamine (DMAPA)

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.
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.
Once all the DMAPA is added, 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.

Comparative Example 3 - Formation of a 1000 M _n PIBSA/DMAPA Quaternary Ammonium Salt using Propylene Oxide (an imide/propylene oxide quat)

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.

Comparative Example 4 - Formation of a 1000 M _n PIBSA/DMAPA Quaternary Ammonium Salt using 1,2-Epoxybutane (an imide/epoxybutane quat)

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.
2-ethylhexanol (136.6 g, 1.05 moles), acetic acid (28.24 g, 0.47 moles) and water (4.76 g, 0.264 moles) are also charged to the 1-liter flask. The batch is then heated to 90 °C, under agitation and nitrogen atmosphere. 1,2-epoxybutane (37.3g, 0.51moles) is added via the syringe pump over 2 hours. The batch is then held for 3 hours at 90 °C before being cooled back to 50 °C. The imide/epoxybutane quat is then decanted into a storage vessel.

Example 5 - Formation of a 1000 M _n PIBSA/DMAPA Quaternary Ammonium Salt using 1,2-Epoxydodecane (an imide/epoxydodecane quat - not according to the invention

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.
2-ethylhexanol (315.4 g, 2.43 moles), 1,2-epoxydodecane (146 g, 0.793 moles), acetic acid (46 g, 0.77 moles), and water are also charged to the 2-liter flask. Agitation is then initiated (200 rpm) and a slow nitrogen purge is introduced. The batch is then heated to 75 °C and maintained at temperature for 4 hours. The imide/epoxydodecane quat is then then cooled before it is transferred into a storage vessel.

Example 6 - Formation of a 1000 M _n PIBSA/DMAPA Quaternary Ammonium Salt using 1,2-Epoxyhexadecane (an imide/epoxyhexadecane quat - not according to the invention

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.

Example 7 - Formation of a 1000 M _n PIBSA/DMAPA Quaternary Ammonium Salt using Glycidol (an imide/glycidol quat)

A 1000 M_n PIBSA/DMAPA quaternizable compound (845 g, 0.78 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.
2-ethylhexanol (315.4 g, 2.43 moles), glycidol (63 g, 0.85 moles), acetic acid (47.3 g, 0.78 moles), and water (8.2 g, 0.45 moles) are also charged to the 2-liter flask. Agitation is then initiated (200 rpm) and a slow nitrogen purge is introduced. The batch is then heated to 75 °C and maintained at temperature for 4 hours. The imide/glycidol quat is then then cooled before it is transferred into a storage vessel.

Example 8 - Formation of 550 M _n Polyisobutylene Succinic Anhydride (PIBSA)

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 Eurotherm™ temperature controller (reaction kit).
Maleic anhydride (632.2 g 6.449 moles) is then charged to the reaction vessel. The batch is agitated under a nitrogen blanket and slowly heated to 203 °C over a 90 minute period. The batch is maintained at 203°C for 24 hours.
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 and ∼ 20% unreacted polyisobutylene is then cooled back to 50 °C and decanted into a storage vessel.

Example 9 - Formation of Quaternizable Compound - 550 M _n PIBSA and Dimethylaminopropylamine (DMAPA)

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.
Once all the DMAPA is added, 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) - not according to the invention

The 550 M_n PIBSA/DMAPA quaternizable compound of Example 9 (475 g, 0.62 moles) 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.
2-ethylhexanol (136 g, 1.05 moles), acetic acid (37.3 g, 0.62 moles) and water (4.4g, 0.24 moles) are also charged to the 1-liter flask. The batch is then heated to 75 °C, under agitation and nitrogen atmosphere. 1,2-epoxybutane (48.9 g, 0.68 moles) is added via the syringe pump over 2 hours. The batch is then held for 3 hours at 75 °C. The imide/epoxybutane quat is then cooled and discharged into a storage vessel.

Example 11 (prophetic) - Formation of a 550 M _n PIBSA/DMAPA Quaternary Ammonium Salt using 1,2-Epoxydodecane (an imide/epoxydodecane quat) - not according to the invention

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) - not according to the invention

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.
2-ethylhexanol (138.0 g, 1.06 moles), glycidol (48.2 g, 0.65 moles), acetic acid (37.2 g, 0.62 moles), and water (4.1 g, 0.22 moles) are also charged to the 1-liter flask. Agitation is then initiated (200 rpm) and a slow nitrogen purge is introduced. The batch is then heated to 75 °C and maintained at temperature for 4 hours. The imide/glycidol quat is then then cooled before it is transferred into a storage vessel.

Example 14 (prophetic) - Formation of 2300 M _n Polyisobutylene Succinic Anhydride (PIBSA)

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 Eurotherm™ temperature controller (reaction kit).
Maleic anhydride (165.5 g, 1.70 moles) is then charged to the reaction vessel. The batch is agitated under a nitrogen blanket and slowly heated to 203 °C over a 90 minute period. The batch is maintained at 203°C for 24 hours.
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.

Example 15 - Formation of Quaternizable Compound - 2300 M _n PIBSA and Dimethylaminopropylamine (DMAPA)

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) - not according to the invention

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.
2-ethylhexanol (145.4 g, 1.12 moles), 1,2-epoxydodecane (51.55 g, 0.28 moles), acetic acid (17.4 g, 0.29 moles), and water (5.6 g, 0.31 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 and 15 minutes. The imide/epoxydodecane quat is then then cooled before it is transferred into a storage vessel.

Example 17 - Formation of a 2300 M _n PIBSA/DMAPA Quaternary Ammonium Salt using 1,2-Epoxyhexadecane (an imide/epoxyhexadecane quat) - not according to the invention

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.
2-ethylhexanol (145.4 g, 1.12 moles), 1,2-epoxyhexadecane (67.4 g, 0.28 moles), acetic acid (17.4 g, 0.29 moles), and water (5.6 g, 0.31 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 and 15 minutes. The imide/epoxyhexadecane quat is then then cooled before it is transferred into a storage vessel.

Example 18 - Formation of a 2300 M _n PIBSA/DMAPA Quaternary Ammonium Salt using Glycidol (an imide/glycidol quat)

The 2300 M_n PIBSA/DMAPA quaternizable compound of Example 15 (550 g, 0.25 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 (175.6 g, 1.35 moles), glycidol (18.85 g, 0.25 moles), acetic acid (15.28 g, 0.25 moles), and water (5 g, 0.27 moles) are also charged to the 1-liter flask. Agitation is then initiated (200 rpm) and a slow nitrogen purge is introduced. The batch is then heated to 90 °C and maintained at temperature for 3 hours. The imide/glycidol quat is then then cooled before it is transferred into a storage vessel.

Demulsification (Water Shedding) Testing

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.
The fuel (80 mL) is then added to a clean, 100 mL-graduated cylinder. A phosphate buffer solution with a pH of 7.0 (20 mL) is then added to the graduated cylinder and the cylinder is stoppered. The cylinder is shaken for 2 minutes at 2 to 3 strokes per second and placed on a flat surface. The volume of the aqueous layer, or water recovery, is then measured at 3, 5, 7, 10, 15, 20, and 30-minute intervals.

The results of the demulsification tests are shown in Table 1 below and in FIG. 1.

Table 1

	3	5	7	10	15	30	Time
Example 4	2.5	8.5	14	18	19	20	Water recovered (mL)
Example 6	11	18	19	20	20	20	Water recovered (mL)
Example 17	2.5	8.5	14	18	19	20	Water recovered (mL)
Example 5	10.5	18	19	20	20	20	Water recovered (mL)
Example 7	0	0	0	2	15	20	Water recovered (mL)
Example 18	7	8	13	15	17	19	Water recovered (mL)
Comparative Example 3	2	2	4	4	5	10	Water recovered (mL)

Deposit Tests - CEC F-23-01 Procedure for Diesel Engine Injector Nozzle Coking Test

Deposit tests are performed using Peugeot S.A.'s XUD 9 engine in accordance with the procedure in CEC F-23-01. For the first deposit test, air flow is measured though clean injector nozzles of the XUD 9 engine using an air-flow rig. The engine is then run on a reference fuel (RF79) and cycled through various loads and speeds for a period of 10 hours to simulate driving and allow any formed deposits to accumulate. The air-flow through the nozzles are measured again using the air-flow rig. The percentage of air flow loss (or flow remaining) is then calculated.
A set of deposit tests are performed using the same steps above, except 10 ppm actives of the epoxide quat are added to the reference fuel. A second set of deposit tests are performed using the same steps above, except 30 ppm actives are added to the reference fuel.
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 4 25.9 74.1

Example 6 13.0 87.0

Example 7 8.6 91.4

Example 18 19.0 81.0

Reference Fuel 80 20
Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about." Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements.
As used herein, 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. However, in each recitation of "comprising" herein, it is intended that 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.
While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. In this regard, the scope of the invention is to be limited only by the following claims. Various preferred features and embodiments of the present invention will now be described with reference to the following numbered paragraphs (paras).

1. A composition comprising an epoxide quaternary ammonium salt ("epoxide quat"), wherein the epoxide quat comprises the reaction product of:
1. a) a quaternizable compound that is the reaction product of:
  1. (i) a hydrocarbyl-substituted acylating agent, wherein the hydrocarbyl-substituent has a number average molecular weight ranging from 100 to 5000, and
  2. (ii) a nitrogen containing compound having an oxygen or nitrogen atom capable of reacting with said hydrocarbyl-substituted acylating agent, and further having at least one quaternizable amino group; and
2. b) a quaternizing agent comprising alcohol functionalized epoxides; C₄ to C₁₄ epoxides; and mixtures thereof.
2. A composition comprising an epoxide quaternary ammonium salt ("epoxide quat"), wherein the epoxide quat comprises the reaction product of:
1. a) a quaternizable compound that is the reaction product of:
  1. (i) a hydrocarbyl-substituted acylating agent, wherein the hydrocarbyl-substituent has a number average molecular weight ranging from 100 to 5000, and
  2. (ii) a nitrogen containing compound having an oxygen or nitrogen atom capable of reacting with said hydrocarbyl-substituted acylating agent, and further having at least one quaternizable amino group; and
2. b) a quaternizing agent comprising alcohol functionalized epoxides; C₄ to C₂₀ epoxides; and mixtures thereof.
3. The composition of any of previous para, wherein the quaternizable amino group is a primary, secondary or tertiary amino group.
4. The composition of any previous para, wherein the hydrocarbyl-substituted acylating agent comprises at least one polyisobutenyl succinic anhydride or polyisobutenyl succinic acid.
5. The composition of any previous para, wherein the reaction in a) is carried out at a temperature of greater than 80, 90, or 100 °C.
6. The composition of any previous para, wherein the reaction in a) is carried out at a temperature of less than 80°C.
7. The composition of any previous para, wherein the quaternizing agent comprises a C₄ to C₁₄ epoxide.
8. The composition of any previous para, wherein the quaternizing agent comprises an alcohol functionalized epoxide.
9. The composition of para 8, wherein the quaternizing agent is glycidol.
10. The composition of para 7, wherein the quaternizing agent is 1,2-epoxyhexadecane.
11. The composition of para 7, wherein the quaternizing agent comprises butylene oxide.
12. The composition of any of any previous para wherein the quaternizing agent is employed in the presence of a protic solvent.
13. The composition of para 12, wherein the protic solvent comprises 2-ethylhexanol, water, and mixtures thereof.
14. The composition of any previous para wherein the quaternizing agent is employed in the presence of an acid.
15. The composition of para 14, wherein the acid is present in the structure of the acylating agent.
16. The composition of any previous para, further comprising at least one other additive.
17. The composition of para 16, wherein the at least one other additive comprises a detergent, a dispersant, a demulsifier, a lubricity agent, a cold flow improver, an antioxidant, or a mixture thereof.
18. The composition of para 16, wherein the at least one other additive comprises at least one hydrocarbyl-substituted succinic acid.
19. The composition of para 16, wherein the at least one other additive comprises at least one hydrocarbyl-substituted quaternary ammonium salt.
20. The composition of para 16, wherein the at least one other additive comprises at least one detergent/dispersant that is an amphiphilic substance 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; (v) Polyoxy-C₂ to C₄ alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups; (vii) Moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups; and/or (viii) Moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono-or polyamines.
21. The composition of either of paras 18 through 20, wherein the hydrocarbyl-substituent is a polyisobutylene having a molecular weight ranging from 100 to 5000.
22. The composition of para 16, wherein the at least one other additive comprises at least one Mannich compound.
23. The composition of any previous para, further comprising a fuel that is liquid at room temperature.
24. The composition of para 23, wherein the fuel is gasoline or diesel.
25. The composition of any of paras 1 to 24 further comprising an oil of lubricating viscosity.
26. A method of operating an internal combustion engine comprising:
1. a) supplying to said engine:
  1. (i) a fuel, wherein said fuel
    1. 1. is liquid at room temperature; and
  2. (ii) has a composition comprising an epoxide quat according to any paras 1 to 24 therein; and
2. b) operating said engine.
27. A method of operating an internal combustion engine comprising:
1. a) supplying to a crankcase of said engine:
  1. (i) an oil of lubricating viscosity; having a composition comprising an epoxide quat according to any paras 1 to 24 therein, and
2. b) operating said engine.
28. The method of para 27 wherein the oil of lubricating viscosity has total sulfated ash of less than 1 wt% and/or a phosphorus content of less than 0.11 wt%.
29. A method of improving water shedding performance of a fuel composition comprising employing a composition comprising an epoxide quat according to any of paras 1 to 24.
30. A method of reducing and/or preventing injector deposits comprising:
1. a) supplying to a fuel injector of said engine:
  1. (i) a fuel, wherein said fuel
    1. 1. is liquid at room temperature; and
    2. 2. has a composition comprising an epoxide quat according to any paras 1 to 24 therein; and
2. b) operating said engine.

Claims

A composition comprising:
a. an oil of lubricating viscosity;

b. an epoxide quaternary ammonium salt ("epoxide quat"), wherein the epoxide quat comprises the reaction product of:
i. a quaternizable compound that is the reaction product of:
1. a hydrocarbyl-substituted acylating agent, wherein the hydrocarbyl-substituent has a number average molecular weight ranging from 100 to 5000, and comprises at least one polyisobutenyl succinic anhydride or polyisobutenyl succinic acid; and

2. a nitrogen containing compound having an oxygen or nitrogen atom capable of reacting with said hydrocarbyl-substituted acylating agent, and further having at least one quaternizable amino group; and

ii. a quaternizing agent comprising alcohol functionalized epoxides, preferably wherein the quaternizing agent is glycidol.
The composition of claim 1, wherein the hydrocarbyl-substituent of said acylating agent has a number average molecular weight of 550.
The composition of any of previous claim, wherein the quaternizable amino group is a primary, secondary or tertiary amino group.
The composition of any of any previous claim wherein the quaternizing agent is employed in the presence of a protic solvent.
The composition of claim 4, wherein the protic solvent comprises 2-ethylhexanol, water, and mixtures thereof.
The composition of any previous claim wherein the quaternizing agent is employed in the presence of an acid.
The composition of claim 6, wherein the acid is present in the structure of the acylating agent.
The composition of any previous claim, further comprising at least one other additive, preferably wherein the at least one other additive comprises a detergent, a dispersant, a demulsifier, a lubricity agent, a cold flow improver, an antioxidant, or a mixture thereof.
The composition of claim 8, wherein the at least one other additive comprises at least one hydrocarbyl-substituted quaternary ammonium salt.
The composition of claim 8, wherein the at least one other additive comprises at least one detergent/dispersant that is an amphiphilic substance 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; (v) Polyoxy-C₂ to C₄ alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups; (vii) Moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups; and/or (viii) Moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono-or polyamines.
The composition of any previous claim, wherein the composition is free or substantially free of a zinc dialkyldithiophosphate.
A method of operating an internal combustion engine comprising:
a. supplying to a crankcase of said engine:
i. an oil of lubricating viscosity; having a composition comprising an epoxide quat according to any claims 1 to 11 therein, and

ii. operating said engine.