Gasoline additive composition for improving engine performance

Abstract

The present disclosure provides a fuel additive comprising a Mannich detergent additive and a Mannich-based quaternary ammonium salt detergent additive that effectively improves engine performance in both port fuel injection engines and in-cylinder direct injection engines.

Description

Technical Field

[0001] The present disclosure relates to fuel additives for spark-ignition engines that provide enhanced engine, intake valve, and / or injector performance, fuel compositions containing such additives, and methods of using such fuel additives in fuel compositions to improve performance. Background Art

[0002] Fuel compositions for vehicles are continuously improved to enhance various properties of the fuel to accommodate their use in newer, more advanced engines, including both gasoline port fuel injection (PFI) engines and gasoline direct injection (GDI) engines. Generally, the improvement of fuel compositions focuses on improving fuel additives and other components used in the fuel. For example, friction modifiers can be added to the fuel to reduce friction and wear in the fuel delivery system of the engine. Other additives can be included to reduce the corrosion potential of the fuel or to improve its conductive properties. Still other additives can be blended with the fuel to improve fuel economy. Engine and fuel delivery system deposits represent another problem for modern internal combustion engines, and thus other fuel additives typically include various deposit control additives to control and / or mitigate engine deposit problems. Thus, fuel compositions generally contain complex mixtures of additives.

[0003] However, challenges still exist when attempting to balance such complex classes of additives. For example, some conventional fuel additives can be beneficial for one property or one type of engine but detrimental to another property of the fuel at the same time. In some cases, fuel additives that are effective in gasoline port fuel injection (PFI) engines do not necessarily provide comparable performance in gasoline direct injection (GDI) engines, and vice versa. In still other cases, fuel additives typically require unreasonably high treatment rates to achieve the desired effect, which often places an undesirable limitation on the available amount of other additives in the fuel composition. Still other fuel additives tend to be expensive and / or difficult to manufacture or incorporate into the fuel. Summary of the Invention

[0004] In one embodiment or method, a fuel additive for a spark ignition engine is provided, the fuel additive comprising a detergent, the detergent comprising one or more Mannich detergent additives and one or more Mannich-based quaternary ammonium salt detergent additives. In one aspect, the one or more Mannich detergent additives comprise the reaction product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more amines. In another aspect, the one or more Mannich-based quaternary ammonium salt detergent additives comprise (i) a Mannich reaction product or derivative thereof having at least one tertiary amino group and prepared from a hydrocarbyl-substituted phenol, cresol or derivative thereof, an aldehyde, and a hydrocarbylamine or polyamine providing the tertiary amino group, and reacted with (ii) a quaternizing agent selected from the group consisting of a carboxylic acid or polycarboxylic acid, an ester, an amide, or a salt or halogen-substituted derivative thereof. In either aspect, about 2 wt% to about 50 wt% of the detergent is one or more Mannich-based quaternary ammonium salt detergent additives.

[0005] The fuel additive of the preceding paragraph may include one or more optional features or embodiments in any combination. These optional features or embodiments may include one or more of the following: wherein about 2 wt% to about 20 wt% of the detergent is one or more Mannich-based quaternary ammonium salt detergent additives; and / or wherein the one or more Mannich detergent additives have the structure of Formula I:

[0006]

[0007] wherein R of Formula I 1 is hydrogen or a C1 to C4 alkyl group, R of Formula I 2 is a hydrocarbyl group having a number average molecular weight of about 500 to about 3000, R of Formula I 3 is a C1 to C4 alkylene or alkenyl group, and R of Formula I 4 and R 5 are independently hydrogen, a C1 to C12 alkyl group or a C1 to C4 alkylaminodi(C1-C12 alkyl) group; and / or wherein R of Formula I 2 is a polyisobutenyl group having a number average molecular weight of about 500 to about 1500; and / or wherein the detergent comprises two Mannich detergent additives, wherein the first Mannich detergent additive has the structure of Formula I, wherein R 4 and R 5 are each a C1 to C12 alkyl group, and the second Mannich detergent additive has the structure of Formula I, wherein R 4 is hydrogen and R 5is a bis(C1-C4)alkylamino C1-C12 alkyl group; and / or wherein the first Mannich detergent additive has the structure of formula Ia and the second Mannich detergent additive has the structure of formula Ib:

[0008]

[0009] wherein each R 1 is independently hydrogen or a C1-C4 alkyl group, each R 2 is independently a hydrocarbyl group having a number average molecular weight of from about 500 to about 3000, R 6 and R 7 are independently C1-C12 alkyl groups; and / or wherein the detergent comprises from about 10 wt% to about 30 wt% of the first Mannich detergent additive and from about 10 wt% to about 30 wt% of the second Mannich detergent additive; and / or wherein the weight ratio of the first Mannich detergent additive to the second Mannich detergent additive is from about 1:1 to about 2:1; and / or wherein one or more Mannich-based quaternary ammonium salt detergent additives have the structure of formula II

[0010]

[0011] wherein R 8 is a hydrocarbyl group, wherein the hydrocarbyl has a number average molecular weight of from about 200 to about 5,000; R 9 is hydrogen or C 1 -C 6 alkyl group; R 10 is hydrogen or is a -C(O)- group or -CH 11 - group which together with R 2 forms a ring structure with the nitrogen atom closest to the aromatic ring; R 11 is hydrogen, C 1 -C 6 alkyl, -(CH 2 ) a -NR 5 R 6 、-(CH 2 ) a -aryl(R 1 )(R 2 )(OR 3 ) or is a -C(O)- group or -CH 10 - group which together with R 2 forms a ring structure with the nitrogen atom closest to the aromatic ring (each of R 5 and R 6 is independently a C1-C12 alkyl group); R 12 is C 1 -C 6alkyl, or together with forms a C1-C6 alkyl-substituted R 13 and R 14 are independently C 1 -C 6 alkyl; a is an integer from 1 to 10, b is an integer selected from 0 or 1, and c is an integer from 0 to 10; X is oxygen or nitrogen; and is an anionic group having the structure R 15 C(O)O wherein R 15 is one of the following: (i) together with R 12 is a C1-C6 alkyl group or (ii) C 1 -C 6 alkyl, aryl, C 1 -C 4 alkylene-C(O)O-R 2 or -C(O)O-R 2 group (R 2 is a C1 to C6 alkyl group); and / or wherein R 8 of formula II is a hydrocarbyl group derived from a polyisobutene polymer or oligomer having a number average molecular weight of about 500 to about 1,500, R 9 of formula II is hydrogen or a methyl group, R 10 and R 11 of formula II are each hydrogen; a is an integer from 1 to 4, and b and c are each 0; and / or wherein R 12 , R 13 and R 14 of formula II are each C 1 -C 6 alkyl, and wherein is an anionic group having the structure wherein R 15 is C 1 -C 6 alkyl, aryl, C 1 -C 4 alkylene-C(O)O-R 2 or -C(O)O-R 2 group; and / or further comprises an alkoxylated alcohol, and wherein the weight ratio of the alkoxylated alcohol to one or more Mannich detergent additives is about 1.0 or less; and / or wherein the alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol or alkyl phenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations thereof; and / or wherein the alkoxylated alcohol is a polyether having the structure of formula VI:

[0012]

[0013] wherein R of formula VI 6 is an aryl group or a straight-chain, branched-chain or cyclic aliphatic group having 5 to 50 carbons, R of formula VI 7 is a C1 to C4 alkyl group, and n is an integer from 5 to 100; and / or wherein the fuel additive comprises from about 20 wt% to about 60 wt% of one or more Mannich detergent additives, from about 1 wt% to about 50 wt% of one or more quaternary ammonium salt detergent additives, and from about 5 wt% to about 30 wt% of an alkoxylated alcohol.

[0014] In another method or embodiment, there is provided herein a gasoline fuel composition comprising at least one detergent, the detergent comprising one or more Mannich detergent additives and one or more Mannich-based quaternary ammonium salt detergent additives. In one aspect, the fuel composition comprises from about 15 ppmw to about 300 ppmw of one or more Mannich detergent additives, wherein the Mannich detergent additive is a reaction product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more amines. In another aspect, the fuel comprises from about 1 ppmw to about 200 ppmw of one or more Mannich-based quaternary ammonium salt detergent additives, wherein the Mannich-based quaternary ammonium salt detergent additive is (i) a Mannich reaction product or a derivative thereof having at least one tertiary amino group and prepared from a hydrocarbyl-substituted phenol, cresol or a derivative thereof, an aldehyde, and a hydrocarbylamine or polyamine providing the tertiary amino group, and reacted with (ii) a quaternizing agent selected from the group consisting of carboxylic acids or polycarboxylic acids, esters, amides or salts thereof or halogen-substituted derivatives thereof. In any aspect, from about 2 wt% to about 50 wt% of the detergent is one or more Mannich-based quaternary ammonium salt detergent additives. In another aspect, the fuel may optionally further comprise from about 5 ppmw to about 150 ppmw of an alkoxylated alcohol. Embodiments of the fuel composition may also include any combination of the optional features or embodiments of the fuel additives as described above and as set forth in the Summary of the Invention.

[0015] In another method or embodiment, a method of reducing deposits in a gasoline engine using any embodiment of the fuel additives or fuel compositions of the present disclosure. In one embodiment, the method includes operating a gasoline engine with a fuel composition that contains a majority of gasoline fuel and a minor amount of a fuel additive by injecting the gasoline fuel via one or more injectors. The fuel additive comprises a detergent, the detergent comprising one or more Mannich detergent additives and one or more Mannich-based quaternary ammonium salt detergent additives. In one aspect, the one or more Mannich detergent additives include the reaction product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more amines. In another aspect, the Mannich-based quaternary ammonium salt detergent additive includes (i) a Mannich reaction product or derivative thereof having at least one tertiary amino group and prepared from a hydrocarbyl-substituted phenol, cresol, or derivative thereof, an aldehyde, and a hydrocarbyl amine or polyamine that provides the tertiary amino group, and reacted with (ii) a quaternizing agent selected from the group consisting of carboxylic acids or polycarboxylic acids, esters, amides, or salts or halogen-substituted derivatives thereof. In any embodiment or aspect of the method, from about 2 wt% to about 50 wt% of the detergent is one or more Mannich-based quaternary ammonium salt detergent additives. In any embodiment or aspect of the method, the fuel additive reduces deposits in the gasoline engine, and wherein the fuel additive reduces deposits in a port fuel injection (PFI) engine, a gasoline direct injection (GDI) engine, or both, and / or wherein the deposits reduced are reduced injector deposits measured by one or more of injector pulse width, injection duration, injector flow rate, or a combination thereof.

[0016] The method of the preceding paragraph may include optional features, embodiments, or method steps in any combination. These optional features, embodiments, or method steps may include one or more of the following: wherein the fuel additive reduces deposits when injected from an injector configured to inject droplets of from about 10 microns to about 30 microns, about 120 microns to about 200 microns, or both; and / or wherein from about 10 wt% to about 20 wt% of the detergent is one or more Mannich-based quaternary ammonium salt detergent additives; and / or wherein one or more of the Mannich detergent additives has the structure of Formula I:

[0017]

[0018] wherein R 1 is hydrogen or a C1 to C4 alkyl group, R 2 is a hydrocarbyl group having a number average molecular weight of from about 500 to about 3000, R 3 is a C1 to C4 alkylene or alkenylene group, and R 4 and R 5Independently hydrogen, a C1 to C12 alkyl group or a di(C1 to C4)alkylamino C1-C12 alkyl group; and / or wherein R 2 is a polyisobutenyl group having a number average molecular weight of from about 500 to about 1500; and / or wherein one or more Mannich base quaternary ammonium salt detergent additives have the structure of formula II

[0019]

[0020] wherein R 8 is a hydrocarbyl group, wherein the hydrocarbyl group has a number average molecular weight of from about 200 to about 5,000; R 9 is hydrogen or C 1 -C 6 alkyl group; R 10 is hydrogen or is a -C(O)- group or -CH 11 - group that together with R 2 forms a ring structure with the nitrogen atom closest to the aromatic ring; R 11 is hydrogen, C 1 -C 6 alkyl, -(CH 2 ) a -NR 5 R 6 、-(CH 2 ) a -aryl(R 1 )(R 2 )(OR 3 ) or is a -C(O)- group or -CH 10 - group that together with R 2 forms a ring structure with the nitrogen atom closest to the aromatic ring (each of R 5 and R 6 is independently a C1 to C12 alkyl group); R 12 is C 1 -C 6 alkyl, or together with forms a C1-C6 alkyl-substituted R 13 and R 14 are independently C 1 -C 6 alkyl; a is an integer from 1 to 10, b is an integer selected from 0 or 1, and c is an integer from 0 to 10; X is oxygen or nitrogen; and is an anionic group having the structure wherein R 15 is one of the following: (i) together with R 12 is a C1-C6 alkyl group or (ii) C 1 -C6 Alkyl, aryl, C 1 -C 4 Alkylene-C(O)O-R 2 Or -C(O)O-R 2 Group (R 2 Is a C1 to C6 alkyl group); and / or wherein R 8 Is a hydrocarbon group derived from a polyisobutene polymer or oligomer, having a number average molecular weight of about 500 to about 1,500, R 9 Is hydrogen or a methyl group, R 10 And R 11 Are each hydrogen; a is an integer from 1 to 4, and b and c are each 0; and / or wherein R 12 、R 13 And R 14 Are each C 1 -C 6 Alkyl, and wherein Is an anionic group having the structure Wherein R 15 Is C 1 -C 6 Alkyl, aryl, C 1 -C 4 Alkylene-C(O)O-R 2 Or -C(O)O-R 2 Group; and / or further comprises an alkoxylated alcohol, and wherein the weight ratio of the alkoxylated alcohol to the Mannich detergent is about 1.0 or less; and / or wherein the alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol or alkyl phenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof or combinations thereof; and / or wherein the alkoxylated alcohol is a polyether having the structure of formula VI:

[0021]

[0022] Wherein R 6 In formula III is an aryl group or a straight-chain, branched-chain or cyclic aliphatic group having 5 to 50 carbons, R 7 In formula III is a C1 to C4 alkyl group, and n is an integer from 5 to 100; and / or wherein the fuel additive comprises about 20 wt% to about 60 wt% of a Mannich detergent, about 1 wt% to about 50 wt% of one or more Mannich-based quaternary ammonium salt detergent additives and optionally about 5 wt% to about 30 wt% of an alkoxylated alcohol; and / or wherein the detergent comprises two Mannich detergent additives, wherein the first Mannich detergent additive has the structure of formula I, wherein R 4 And R 5Each is a C1 to C12 alkyl group, and the second Mannich detergent additive has the structure of formula I, where R 4 is hydrogen and R 5 is a bis(C1 to C4)alkylamino C1-C12 alkyl group; and / or where the first Mannich detergent additive has the structure of formula Ia and the second Mannich detergent additive has the structure of formula Ib:

[0023]

[0024] where each R 1 is independently hydrogen or a C1 to C4 alkyl group, each R 2 is independently a hydrocarbyl group having a number average molecular weight of from about 500 to about 3000, R 6 and R 7 are independently C1 to C12 alkyl groups; and / or where the detergent comprises from about 10 wt% to about 30 wt% of the first Mannich detergent additive and from about 10 wt% to about 30 wt% of the second Mannich detergent additive; and / or where the weight ratio of the first Mannich detergent additive to the second Mannich detergent additive is from about 1:1 to about 2:1.

[0025] In yet another method or embodiment, there is provided the use of any embodiment of the fuel additives or fuel compositions of the present disclosure for reducing deposits in a gasoline engine, and wherein the use comprises any embodiment of the fuel additive or the fuel composition for reducing deposits in a port fuel injection (PFI) engine, a gasoline direct injection (GDI) engine, or both, and / or wherein the deposits being reduced are reduced injector deposits measured by one or a combination of injector pulse width, injection duration, and injector flow rate. The reduced deposits can be intake valve deposits measured by ASTM D6201 and / or injector cleanliness measured by any method as set forth in the examples herein and at least as described in the following: Smith, S. and Imoehl, W., “Measurement and Control of Fuel Injector Deposits in Direct Injection Gasoline Vehicles,” SAE Technical Paper 2013-01-2616, 2013, doi:10.4271 / 2013-01-2616; and / or Shanahan, C., Smith, S. and / or Sears, B., “A General Method for Fouling Injectors in Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance,” SAE Int. J. Fuels Lubr. 10(3):2017, doi:10.4271 / 2017-01-2298, which are incorporated herein by reference. DETAILED DESCRIPTION

[0026] The present disclosure provides a fuel additive that includes a detergent of one or more Mannich detergent additives and one or more Mannich-based quaternary ammonium salt detergent additives in certain weight ratios to provide improved engine and / or injector performance in both port fuel injection (PFI) engines and gasoline direct injection (GDI) engines. In some methods, the fuel additive may further include an alkoxylated alcohol, and when the alkoxylated alcohol is included, the fuel additive may further include a specific ratio of the alkoxylated alcohol to one or more Mannich detergents. Also provided herein are fuel compositions that include the novel fuel additive combinations and methods of using or combusting a fuel that includes the fuel additive combinations herein to achieve improved engine, intake valve, and / or injector performance. As described below, one or more Mannich detergent additives include the reaction product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more amines; and one or more quaternary ammonium salt detergent additives are in the form of Mannich-based quaternary ammonium salt detergent additives and include (i) a Mannich reaction product or a derivative thereof that has at least one tertiary amino group and is prepared from a hydrocarbyl-substituted phenol, cresol, or a derivative thereof, an aldehyde, and a hydrocarbylamine or polyamine that provides the tertiary amino group, and is reacted with (ii) a quaternizing agent selected from the group consisting of a carboxylic acid or polycarboxylic acid, an ester, an amide, or a salt thereof or a halogen-substituted derivative thereof. In a preferred embodiment, about 2 wt% to about 50 wt% of the detergent is one or more Mannich-based quaternary ammonium salt detergent additives. As shown in the examples herein, the Mannich detergent alone or the Mannich-based quaternary ammonium salt detergent alone provides little or only moderate cleaning performance in a GDI engine or a PFI engine, but when both the Mannich detergent and the Mannich-based quaternary ammonium salt detergent are combined in a fuel additive in certain ratios, surprisingly enhanced cleaning is achieved in both GDI engines and PFI engines.

[0027] In aspects or embodiments of the present disclosure, improved engine, intake valve, and / or injector performance of the fuel additive combinations herein can include one or more of the following: controlling or reducing fuel injector deposits, controlling or reducing intake valve deposits, controlling or reducing combustion chamber deposits, and / or controlling or reducing intake valve sticking in PFI engines, GDI engines, or both types of engines. Improved injector performance can also be one or more of improved fuel flow, improved fuel economy, and / or improved engine efficiency as determined by one or more of injector pulse width, injection duration, and / or injector flow rate. Reduced deposits can be intake valve deposits measured by ASTM D6201 and / or injector cleanliness measured by any method as set forth in the examples herein and at least as described in the following: Smith, S. and Imoehl, W., “Measurement and Control of Fuel Injector Deposits in Direct Injection Gasoline Vehicles,” SAE Technical Paper 2013-01-2616, 2013, doi:10.4271 / 2013-01-2616; and / or Shanahan, C., Smith, S. and / or Sears, B., “A General Method for Fouling Injectors in Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance,” SAE Int. J. Fuels Lubr. 10(3):2017, doi:10.4271 / 2017-01-2298, which are incorporated herein by reference.

[0028] Mannich detergent

[0029] In one aspect, the fuel additives and fuels herein first comprise one or more Mannich detergents. Suitable Mannich detergents include reaction products of hydrocarbon-substituted (or alkyl-substituted) hydroxyaromatic compounds or phenolic compounds, one or more aldehydes, and one or more amines, as discussed in more detail below.

[0030] In one method, the hydrocarbyl or alkyl substituent of the hydroxyaromatic compound can include a long-chain hydrocarbyl or alkyl group on the benzene ring of the hydroxyaromatic compound and can be derived from an olefin or polyolefin having a number average molecular weight (Mn) of about 500 to about 3000, preferably about 700 to about 2100, as determined by gel permeation chromatography (GPC) using polystyrene as a reference. In some methods, the polyolefin can also have a polydispersity (weight average molecular weight / number average molecular weight) of about 1 to about 10 (in other cases about 1 to about 4 or about 1 to about 2), as determined by GPC using polystyrene as a reference.

[0031] Alkylation of the hydroxyaromatic compound or phenolic compound is generally carried out in the presence of an alkylation catalyst at a temperature in the range of about 0 °C to about 200 °C, preferably 0 °C to about 100 °C. Acidic catalysts are generally used to facilitate Friedel-Crafts alkylation. Typical catalysts for commercial production include sulfuric acid, BF 3 , aluminum phenoxide, methanesulfonic acid, cation exchange resins, acidic clays, and modified zeolites.

[0032] Polyolefins for alkyl-substituted hydroxyaromatic compounds suitable for forming Mannich detergents include polypropylene, polybutene, polyisobutene, butene, and / or copolymers of butene and propylene, copolymers of butene and / or isobutene and / or propylene, and one or more monoolefin comonomers copolymerizable therewith (e.g., ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.), wherein the copolymer molecules contain at least 50 wt% of butene and / or isobutene and / or propylene units. Any comonomer polymerized with propylene or butene can be aliphatic and can also contain non-aliphatic groups, such as styrene, o-methylstyrene, p-methylstyrene, divinylbenzene, etc., if desired. Thus, the resulting polymers and copolymers for forming alkyl-substituted hydroxyaromatic compounds are substantially aliphatic hydrocarbon polymers.

[0033] Polybutene is preferably used to form the hydrocarbyl-substituted hydroxyaromatic compounds or phenolic compounds herein. Unless otherwise specified herein, the term "polybutene" is used in its general sense to include polymers made from "pure" or "substantially pure" 1-butene or isobutene, as well as polymers made from mixtures of two or all three of 1-butene, 2-butene, and isobutene. Commercial grades of such polymers can also contain small amounts of other olefins. So-called highly reactive polyisobutenes having a relatively high proportion of polymer molecules with terminal vinylidene groups are also suitable for forming long-chain alkylated phenol reactants. Suitable highly reactive polyisobutenes include those polyisobutenes that contain at least about 20%, preferably at least 50%, and more preferably at least 70% of the more reactive methylvinylidene isomers. Suitable polyisobutenes include those using BF 3Polyisobutene prepared with a catalyst. The preparation of such polyisobutenes in which the methylvinylidene isomer is present in a high percentage of the total composition is described in US 4,152,499 and US 4,605,808, both of which are incorporated herein by reference.

[0034] In some methods or embodiments, Mannich detergents can be prepared from alkylphenols or alkylcresols. However, other phenolic compounds can be used, including alkyl-substituted derivatives of resorcinol, hydroquinone, catechol, hydroxydiphenyl, benzylphenol, phenylethylphenol, naphthol, tolylnaphthol, and the like. Preferred for the preparation of Mannich detergents are polyalkylphenol and polyalkylcresol reactants, such as polypropylphenol, polybutylphenol, polypropylcresol, and polybutylcresol, wherein the alkyl group has a number average molecular weight of about 500 to about 3000 or about 500 to about 2100 as measured by GPC using polystyrene as a reference, and the most preferred alkyl group is polybutyl derived from polyisobutene, which has a number average molecular weight in the range of about 700 to about 1300 as measured by GPC using polystyrene as a reference.

[0035] The preferred configuration of the alkyl-substituted hydroxyaromatic compound is the para-substituted monoalkylphenol or para-substituted monoalkyl-o-cresol configuration. However, any hydroxyaromatic compound that readily reacts in the Mannich condensation reaction can be employed. Thus, Mannich products made from hydroxyaromatic compounds having only one cycloalkyl substituent or two or more cycloalkyl substituents are suitable for forming the detergent additive. The alkyl substituent may contain some residual unsaturated groups but is generally a substantially saturated alkyl group.

[0036] In the method or embodiment, representative amine reactants suitable for forming the Mannich detergents herein include, but are not limited to, alkylene polyamines having at least one suitably reactive primary or secondary amino group in the molecule. Other substituents such as hydroxy, cyano, amido, etc. may be present in the polyamine. In one embodiment, the alkylene polyamine is a polyethylene polyamine. Suitable alkylene polyamine reactants include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and mixtures of such amines, the nitrogen content of which corresponds to the formula H 2 N--(A-NH--) n H of the alkylene polyamine, wherein A in this formula is a divalent vinyl or propylene group, and n is an integer from 1 to 10, preferably from 1 to 4. The alkylene polyamine can be obtained by reacting ammonia with a dihaloalkane such as a dichloroalkane.

[0037] The amine can also be an aliphatic diamine having a primary or secondary amino group and at least one tertiary amino group in the molecule. Examples of suitable polyamines include N,N,N",N"-tetraalkyl dialkylene triamines (two terminal tertiary amino groups and one central secondary amino group), N,N,N',N"-tetraalkyl trialkylene tetramines (one terminal tertiary amino group, two internal tertiary amino groups and one terminal primary amino group), N,N,N',N",N'"-pentaalkyl trialkylene tetramines (one terminal tertiary amino group, two internal tertiary amino groups and one terminal secondary amino group), N,N'-dialkylamines, N,N-dihydroxyalkyl-α,ω-alkylenediamines (one terminal tertiary amino group and one terminal primary amino group), N,N,N'-trihydroxyalkyl-α,ω-alkylenediamines (one terminal tertiary amino group and one terminal secondary amino group), tris(dialkylaminoalkyl)aminoalkylmethanes (three terminal tertiary amino groups and one terminal primary amino group) and similar compounds, where these alkyl groups are the same or different and generally each contain no more than about 12 carbon atoms, and preferably each contains 1 to 4 carbon atoms. Most preferably, these alkyl groups are methyl and / or ethyl. Preferred polyamine reactants are N,N-dialkyl-α,ω-alkylenediamines, such as those having 3 to about 6 carbon atoms in the alkylene group and 1 to about 12 carbon atoms in each alkyl group, these alkyl groups being most preferably the same, but may be different. Exemplary amines can include N,N-dimethyl-1,3-propanediamine and / or N-methylpiperazine.

[0038] Examples of polyamines having a reactive primary or secondary amino group capable of participating in the Mannich condensation reaction and at least one sterically hindered amino group that cannot directly participate in the Mannich condensation reaction to any significant extent include N-(tert-butyl)-1,3-propanediamine, N-neopentyl-1,3-propanediamine, N-(tert-butyl)-1-methyl-1,2-ethanediamine, N-(tert-butyl)-1-methyl-1,3-propanediamine and 3,5-di(tert-butyl)aminoethylpiperazine.

[0039] In the method or embodiment, representative aldehydes for preparing the Mannich detergents herein include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, heptanal, stearaldehyde. Aromatic aldehydes that can be used include benzaldehyde and salicylaldehyde. Illustrative heterocyclic aldehydes for the present invention are furfural and thiophene aldehyde and the like. Also usable are formaldehyde-yielding reagents such as paraformaldehyde, or aqueous formaldehyde solutions such as formalin. Most preferred is formaldehyde or formalin.

[0040] The condensation reaction between an alkylphenol, a specific amine, and an aldehyde can be carried out at a temperature in the range of typically about 40 °C to about 200 °C. The reaction can be carried out in bulk (without a diluent or solvent) or in a solvent or diluent. Water is removed during the reaction and can be removed by azeotropic distillation. Generally, the Mannich reaction product is formed by reacting an alkyl-substituted hydroxyaromatic compound, an amine, and an aldehyde in a molar ratio of 1.0:0.5 - 2.0:1.0 - 3.0, respectively. Suitable Mannich base detergents include those detergents taught in the following patents: US 4,231,759; US 5,514,190; US 5,634,951; US 5,697,988; US 5,725,612; and 5,876,468, the disclosures of which are incorporated herein by reference.

[0041] In other methods or embodiments, the Mannich detergents suitable for the fuel additives herein can have the structure of Formula I:

[0042]

[0043] wherein R of Formula I 1 and R 2 one of them is hydrogen or a C1 to C4 alkyl group, and the other of R 1 and R 2 is a hydrocarbyl group having a number average molecular weight of about 500 to about 3000,

[0044] R of Formula I 3 is a C1 to C4 alkylene or alkenyl linking group, and R of Formula I 4 and R 5 are independently hydrogen, a C1 to C12 alkyl group, or a mono(C1 to C4)alkylamino C1-C12 alkyl group or a di(C1 to C4)alkylamino C1-C12 alkyl group. In one aspect, R of Formula I 1 is hydrogen or a C1 to C4 alkyl group, and R of Formula I 2 is a hydrocarbyl group having a number average molecular weight of about 500 to about 3000 (or about 500 to about 2100, or about 500 to about 1800, or about 500 to about 1500). In another aspect, R of Formula I 1 is hydrogen or a C1 to C4 alkyl group, and R of Formula I 2 is a polyisobutenyl group having a number average molecular weight of about 500 to about 1500.

[0045] In other methods or embodiments, the detergent can comprise at least two Mannich detergent additives. In this optional embodiment, the first Mannich detergent additive can have the structure of Formula I, wherein R 4 and R 5each being a C1 to C12 alkyl group (preferably a C3 to C6 alkyl group), and the second Mannich detergent additive may have the structure of formula I, where R 4 is hydrogen and R 5 is a bis(C1 to C4)alkylamino C1-C12 alkyl group. More specifically, the first Mannich detergent additive may have the structure of formula Ia and the second Mannich detergent additive has the structure of formula Ib:

[0046]

[0047] where each R 1 is independently hydrogen or a C1 to C4 alkyl group, each R 2 is independently a hydrocarbyl group having a number average molecular weight of from about 500 to about 3000 (or other ranges as discussed above), and R 6 and R 7 are independently C1 to C12 alkyl groups (preferably, C1 to C6 alkyl groups, or more preferably, C1 to C4 alkyl groups).

[0048] If the detergent comprises a first Mannich detergent additive and a second Mannich detergent additive, the detergent may comprise from about 10 wt% to about 30 wt% of the first Mannich detergent additive and from about 10 wt% to about 30 wt% of the second Mannich detergent additive. In other methods and if the detergent comprises a first Mannich detergent additive and a second Mannich detergent additive, the weight ratio of the first Mannich detergent additive to the second Mannich detergent additive is from about 1:1 to about 2:1.

[0049] The fuel additive or additive package may comprise from about 20 wt% to about 60 wt% of one or more of the above Mannich detergents, from about 22 wt% to about 45 wt% of one or more Mannich detergents or from about 25 wt% to about 40 wt% of one or more Mannich detergents (based on the total weight of the active Mannich detergents in the fuel additive). When blended into a gasoline fuel, the fuel composition may comprise in the fuel composition from about 10 ppmw to about 300 ppmw of the above Mannich detergents, from about 25 ppmw to about 155 ppmw, from about 45 ppmw to about 125 ppmw or from about 55 ppmw to about 125 ppmw of the Mannich detergents (active Mannich detergent treatment rate). In some embodiments, the fuel additives herein comprise a single type of Mannich detergent, or as discussed above, the fuel additives herein may comprise at least two Mannich detergents.

[0050] Mannich-based quaternary ammonium salt detergent

[0051] The Mannich quaternary ammonium salt detergent additives of the present invention are derived from Mannich reaction products having at least terminal tertiary amines, and then the tertiary amines are quaternized with a suitable quaternizing agent. For example, one or more Mannich quaternary ammonium salt detergent additives of the present invention include (i) a Mannich reaction product or a derivative thereof, which Mannich reaction product or derivative has at least one tertiary amino group and is prepared from a phenol, cresol or a derivative thereof substituted by a hydrocarbon group, an aldehyde, and a hydrocarbon amine or polyamine providing the tertiary amino group, and reacted with (ii) a quaternizing agent selected from the group consisting of carboxylic acids or polycarboxylic acids, esters, amides or their salts or halogen-substituted derivatives thereof.

[0052] In one embodiment, an exemplary Mannich quaternary ammonium salt compound has the structure of Formula II

[0053]

[0054] wherein R 8 is a hydrocarbon group, wherein the number average molecular weight of the hydrocarbon group is from about 200 to about 5,000; R 9 is hydrogen or C 1 -C 6 alkyl group; R 10 is hydrogen or a -C(O)- group or -CH 11 - group that together with R 2 forms a ring structure with the nitrogen atom closest to the aromatic ring; R 11 is hydrogen, C 1 -C 6 alkyl, -(CH 2 ) a -NR 5 R 6 、-(CH 2 ) a -aryl(R 1 )(R 2 )(OR 3 ) or is one of a -C(O)- group or -CH 10 - group that together with R 2 forms a ring structure with the nitrogen atom closest to the aromatic ring; R 12 is C 1 -C 6 alkyl, or together with forms a C1-C6 alkyl-substituted R 13 and R 14 independently are C 1 -C 6 alkyl; a is an integer from 1 to 10, b is an integer selected from 0 or 1, and c is an integer from 0 to 10; X is oxygen or nitrogen; and has the structure an anionic group, where R 15 is one of the following: (i) together with R 5 is a C1-C6 alkyl group or (ii) an alkyl, aryl or –C(O)O-R 2 group. Preferably, R 10 is hydrogen, a is from 1 to 4 (most preferably 3), b is 0, c is 0, and each of R 12 , R 13 and R 14 is a C1 to C4 (preferably C1) alkyl group.

[0055] The Mannich reaction product is first obtained from a hydrocarbyl-substituted hydroxyaromatic compound. Representative hydrocarbyl-substituted hydroxyaromatic compounds suitable for forming the Mannich-based quaternary salt additives herein may include compounds of formula III

[0056]

[0057] where each R is independently hydrogen, a C1-C4 alkyl group or a hydrocarbyl substituent having a number average molecular weight (Mn) in the range of about 300 to about 5,000 (in other methods, about 300 to about 2,000, especially about 500 to about 1,500) as determined by gel permeation chromatography (GPC). In some methods, at least one R is hydrogen and one R is a hydrocarbyl substituent as defined above.

[0058] In some methods, suitable hydrocarbyl substituents may include polyolefin polymers or copolymers, such as polypropylene, polybutene, polyisobutene and ethylene-α-olefin copolymers. Examples include polymers or copolymers of butene and / or isobutene and / or propylene, and one or more monoolefin comonomers (e.g., ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.), where the copolymer may contain at least 50 wt% of butene and / or isobutene and / or propylene units. The comonomer polymerized with propylene or such butene may be aliphatic or may contain non-aliphatic groups, such as styrene, o-methylstyrene, p-methylstyrene, divinylbenzene, etc. The polyolefin polymer hydrocarbyl substituent may have at least 20%, in some cases at least 50%, and in other cases at least 70% of the olefin double bonds at the terminal positions on the carbon chain as highly reactive vinylidene isomers.

[0059] Polybutene is a useful hydrocarbyl substituent for hydroxyaromatic compounds. The polybutene substituent can include 1-butene or isobutene, and polymers made from mixtures of two or all three of 1-butene, 2-butene, and isobutene. Polyisobutene is another suitable hydrocarbyl substituent for hydroxyaromatic compounds herein. A highly reactive polyisobutene having a relatively high proportion of polymer molecules with terminal vinylidene groups, such as at least 20% of the total terminal olefin double bonds in the polyisobutene comprise alkyl vinylidene isomers, in some cases at least 50%, and in other cases at least 70%, is formed by a method such as described in U.S. Patent No. 4,152,499, which is suitable for forming polyolefins for hydrocarbyl-substituted hydroxyaromatic reactants. Also suitable for forming the long-chain substituted hydroxyaromatic reactants herein are ethylene α-olefin copolymers having a number average molecular weight of 500 to 3,000, wherein at least about 30% of the polymer chains contain terminal ethylenic unsaturated groups.

[0060] In one embodiment, the hydrocarbyl-substituted hydroxyaromatic compound has one R that is H, one R that is a C1-C4 alkyl group (a methyl group in some methods), and one R that is a hydrocarbyl substituent having an average molecular weight in the range of about 300 to about 2,000, such as a polyisobutene substituent. In other embodiments, the hydrocarbyl-substituted hydroxyaromatic compound can be obtained by alkylating o-cresol with a high molecular weight hydrocarbyl polymer, such as a hydrocarbyl polymer having a number average molecular weight of about 300 to about 2,000, to provide an alkyl-substituted cresol. In some cases, o-cresol is alkylated with a polyisobutene having a number average molecular weight of about 300 to about 2,000 to provide a polyisobutene-substituted cresol. In other cases, o-cresol is alkylated with a polyisobutene (PIB) having a number average molecular weight of about 500 to about 1,500 to provide a polyisobutene-substituted cresol (PIB-cresol).

[0061] In other methods, the hydrocarbyl-substituted hydroxyaromatic compound can be obtained by alkylating o-phenol with a high molecular weight hydrocarbyl polymer, such as a hydrocarbyl polymer group having a number average molecular weight of about 300 to about 2,000, to provide an alkyl-substituted phenol. In one embodiment, o-cresol is alkylated with a polybutene having a number average molecular weight of about 500 to about 1,500 to provide a polybutene-substituted cresol.

[0062] The alkylation of the hydroxyaromatic compound can be carried out in the presence of an alkylation catalyst, such as a Lewis acid catalyst (e.g., BF 3 or AlCl 3)It is carried out at a temperature of about 30 °C to about 200 °C in the presence of []. For polyolefins used as hydrocarbyl substituents, they can have a polydispersity (Mw / Mn) of about 1 to about 4, and in other cases, about 1 to about 2, as determined by GPC. Suitable methods for alkylating hydroxyaromatic compounds are described in GB 1,159,368 or US 4,238,628; US 5,300,701 and US 5,876,468, which are incorporated herein by reference in their entirety.

[0063] Representative aldehyde sources for preparing the Mannich base intermediates herein include aliphatic aldehydes, aromatic aldehydes, and / or heterocyclic aldehydes. Suitable aliphatic aldehydes can include C1 to C6 aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and hexanal. Exemplary aromatic aldehydes can include benzaldehyde and salicylaldehyde, and exemplary heterocyclic aldehydes can include furfural and thiophene aldehyde. In some cases, reagents that generate formaldehyde (such as paraformaldehyde) or aqueous formaldehyde solutions (such as formalin) can also be used to form the Mannich-based tertiary amines herein. Most preferably, formaldehyde and / or formalin are used.

[0064] Hydrocarbyl polyamines suitable for the Mannich products herein include those having at least one primary amine and at least one terminal tertiary amine. In one method, the hydrocarbyl polyamine has the structure R 9 R 10 N-[CH 2 a -X b -[CH 2 c -NR 9 R 10 wherein R 9 and R 10 are independently hydrogen or C1 to C6 alkyl groups, a pair of R 9 and R 10 form a tertiary amine, X is oxygen or nitrogen, a is an integer from 1 to 10, b is 0 or 1, and c is an integer from 0 to 10. Suitable exemplary tertiary amines for forming the fuel additives herein can be selected from 3-(2-(dimethylamino)ethoxy)propylamine, N,N-dimethyldipropenyltriamine, dimethylaminopropylamine, and / or mixtures thereof.

[0065] In one embodiment, the Mannich-based quaternary ammonium salt detergent herein is obtained from a tertiary amine having the structure of formula IV

[0066]

[0067] wherein a is an integer from 1 to 10 (preferably an integer from 2 to 4), and R 16 and R 17 ​​Independently C1 to C10 alkyl or hydrocarbon groups (preferably C1 to C4 alkyl groups). In other embodiments, the Mannich-based quaternary ammonium salt detergents herein are obtained from tertiary amines having the structure of formula V

[0068]

[0069] wherein A is a hydrocarbon linking group having from 1 to 10 total carbon units and optionally containing one or more of its carbon units independently replaced by a divalent moiety selected from the group consisting of: -O-, -N(R')-, -C(O)-, -C(O)O- and -C(O)NR', and R 16 and R 17 are independently alkyl groups containing from 1 to 8 carbon atoms; and R' is independently hydrogen or a group selected from C1-C6 aliphatic, phenyl or alkylphenyl. In one method, the selected amine of formula IV or V is at least a diamine or triamine having a terminal primary amino group for the Mannich reaction at one end and a terminal tertiary amine for reaction with a quaternizing agent at the other end. In other optional methods, A contains from 1 to 6 carbon units, wherein one of its carbon units is optionally replaced by an -O- or -NH- group. The hydrocarbon linking group A may optionally have from 1 to 4 carbon units replaced by the divalent moieties described above, which divalent moieties are preferably -O- or -NH- groups. In other optional methods, 1 to 2 carbon units of the hydrocarbon linking group A are replaced by the divalent moieties described herein and 1 carbon unit of the hydrocarbon linking group A in still further optional methods. As will be understood, in these optional methods, the remainder of the hydrocarbon linking group A is preferably carbon atoms. In such optional methods, the number of carbon atoms on either side of the replaced divalent moiety need not be equal, meaning that the hydrocarbon chain between the terminal primary amino group and the terminal tertiary amine need not be symmetric with respect to the replaced divalent moiety.

[0070] To prepare the Mannich-based quaternary ammonium salt detergents herein, the Mannich reaction of the selected polyamine, hydrocarbon-substituted hydroxyaromatic compound and aldehyde as described above is first carried out at a temperature of from about 30 °C to about 200 °C. The reaction can be carried out in bulk (without diluent or solvent) or in a solvent or diluent. Water is removed during the reaction and can be removed by azeotropic distillation. For example, when removing the water evolved in the reaction, the temperature generally rises, such as to about 150 °C. Typical reaction times are in the range of from about 3 hours to about 4 hours, but longer or shorter times can be used as needed or desired.

[0071] An exemplary Mannich reaction can begin by adding a hydrocarbyl-substituted hydroxyaromatic component together with a suitable solvent to a reaction vessel to obtain a blend. The blend is mixed under an inert atmosphere. Next, when the blend is homogeneous and at a moderate temperature, such as about 40 °C to about 45 °C, a polyamine is added. Then, a selected aldehyde, such as formaldehyde, is added. The temperature is increased, such as to about 45 °C to about 50 °C, and the temperature can be further increased to less than 100 °C, such as about 80 °C, and maintained at that temperature for about 30 minutes to about 60 minutes. Then distillation can be carried out using a Dran-Stark water separator or an equivalent device, and the temperature is set to about 130 °C to about 150 °C, it being understood that distillation can be started after a period of time to bring the reaction mixture to about 95 °C to 105 °C. The temperature is maintained at the selected elevated temperature for a sufficient length of time, which can be about an additional 2 hours to about 2.5 hours to produce a Mannich-based tertiary amine. Other suitable Mannich reaction protocols can also be used to prepare the intermediate Mannich-based tertiary amine.

[0072] The Mannich-based tertiary amine so formed is then alkylated or quaternized with a suitable alkylating or quaternizing agent. In one embodiment, a suitable alkylating or quaternizing agent is a carboxylic acid hydrocarbyl ester, such as a carboxylic acid alkyl ester. In such methods, the quaternizing agent can be a carboxylic acid alkyl ester selected from oxalic acid alkyl esters, salicylic acid alkyl esters, and combinations thereof. In one aspect, the alkyl group of the carboxylic acid alkyl ester can contain 1 to 6 carbon atoms and is preferably a methyl group. Particularly useful alkylation or quaternization with a carboxylic acid alkyl ester can be dimethyl oxalate or methyl salicylate. The amount of the carboxylic acid alkyl ester relative to the amount of the tertiary amine reactant can be from about 10:1 to about 1:10, for example, a molar ratio of about 3:1 to about 1:3.

[0073] For alkylation with a carboxylic acid alkyl ester, it may be necessary for the corresponding acid of the carboxylic ester to have a pKa of less than 4.2. For example, the corresponding acid of the carboxylic ester can have a pKa of less than 3.8, such as less than 3.5, with a pKa of less than 3.1 being particularly desirable. Examples of suitable carboxylic esters can include, but are not limited to, maleic acid esters, citric acid esters, fumaric acid esters, phthalic acid esters, 1,2,4-benzenetricarboxylic acid esters, 1,2,4,5-benzenetetracarboxylic acid esters, nitrobenzoic acid esters, nicotinic acid esters, oxalic acid esters, glycine esters, and salicylic acid esters. As described above, preferred carboxylic esters include oxalic acid esters, salicylic acid esters, and combinations thereof.

[0074] The Mannich quaternary ammonium salts of the present disclosure may have the structure of Formula II and may be derived from the following reaction: (i) a Mannich reaction product or a derivative thereof, which has at least one tertiary amino group and is prepared from a phenol, cresol or a derivative thereof substituted by a hydrocarbyl group, an aldehyde, and a hydrocarbyl polyamine providing the tertiary amino group, and reacted with (ii) a quaternizing agent as discussed above, and the quaternizing agent is selected from the group consisting of a carboxylic acid or a polycarboxylic acid, an ester, an amide, or a salt thereof or a halogen-substituted derivative thereof.

[0075] In one embodiment or method, the quaternary ammonium salt fuel additive has the structure of Formula II, wherein R 8 is a hydrocarbyl group derived from a polyisobutene polymer or oligomer having a number average molecular weight of 500 to 1,500, R 9 is hydrogen or a methyl group, R 10 and R 11 are each hydrogen; a is an integer from 1 to 4, and b and c are each 0. In some methods, when the quaternizing agent is an alkyl carboxylate, such as dimethyl oxalate or methyl salicylate, the of the Mannich quaternary ammonium salt is an anionic group having the structure 15 wherein R 2 is an alkyl, aryl or -C(O)O-R

[0076]

[0077] In the embodiments or methods herein, the detergent comprises from about 2 wt% to about 50 wt% of the above-mentioned Mannich-based quaternary ammonium salt detergent additive, and more preferably, the detergent comprises from about 2 wt% to about 20 wt% of one or more quaternary ammonium salt detergent additives, or more preferably, from about 10 wt% to about 20 wt% (based on the total weight of the Mannich detergent and the Mannich-based quaternary salt detergent). The fuel additive or additive package may comprise from about 1 wt% to about 50 wt% of the above-mentioned Mannich-based quaternary ammonium detergent additive, from about 20 wt% to about 50 wt% of the Mannich-based quaternary ammonium detergent, or from about 25 wt% to about 40 wt% of the Mannich-based quaternary ammonium detergent (based on the total weight of the active Mannich-based quaternary ammonium detergent in the fuel additive). When blended into a gasoline fuel, the fuel composition may comprise in the fuel composition from about 1 ppmw to about 200 ppmw of the above-mentioned Mannich-based quaternary ammonium detergent, from about 4 ppmw to about 100 ppmw or from about 7 ppmw to about 50 ppmw of the Mannich-based quaternary ammonium detergent (active quaternary detergent treatment rate).

[0078] Alkoxylated alcohol

[0079] The fuel additive or fuel of the present disclosure may also comprise one or more optional alkoxylated alcohols. The alkoxylated alcohol is preferably a polyether prepared by reacting a long-chain alkyl alcohol or alkylphenol with an alkylene oxide. By one method, the alkoxylated alcohol can be one or more hydrocarbyl-terminated or hydrocarbyl-capped poly(alkylene oxide) polymers. Its hydrocarbyl moiety can be an aryl or aliphatic group, and is preferably a straight-chain, branched-chain or cyclic aliphatic chain, and most preferably a straight-chain aliphatic chain. In one method, the alkoxylated alcohol can have the structure of Formula VIa, VIb and / or VIc:

[0080]

[0081] wherein R in the above Formula VI structure 6 is an aryl group or a straight-chain, branched-chain or cyclic aliphatic group and preferably has 5 to 50 carbons (or 5 to 30 carbons), or can be -C m H 2m+1 group, wherein m is an integer of 12 or greater, and R in the above Formula VI structure 7 is a C1 to C4 alkyl group, and n is an integer from 5 to 100 (or as further discussed below).

[0082] In some methods, suitable alkoxylated alcohols are derived from lower alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, and combinations thereof. Preferably, the lower alkylene oxide is propylene oxide or butylene oxide or a copolymer of ethylene oxide, propylene oxide and butylene oxide (and any combination thereof). In another method, the alkylene oxide is propylene oxide. Any copolymer of such alkylene oxides can be a random or block copolymer. In one method, the alkoxylated alcohol can be terminated or capped with an aryl, alkyl or hydrocarbyl group, and can include one or more aryl or straight-chain, branched-chain or cyclic aliphatic C5 to C30-capped alkoxylated alcohols, and in other methods, C16 to C18 (or blends thereof)-capped alkoxylated alcohols having 5 to 100, 10 to 80, 20 to 50 or 22 to 32 alkylene oxide repeat units (i.e., the integer n in the above formula). In some methods, the alkoxylated alcohol can have a weight average molecular weight of about 1300 to about 2600, and in other methods, about 1600 to about 2200.

[0083] In some methods, the aliphatic hydrocarbon group-terminated alkoxylated alcohols can include from about 20 wt% to about 70 wt% (in another method, from about 30 wt% to about 50 wt%) of an aliphatic C16 alkoxylated alcohol having 24 to 32 alkylene oxide repeat units, and / or can include from about 30 wt% to about 80 wt% (in another method, from about 50 wt% to about 70 wt%) of an aliphatic C18 alkoxylated alcohol having 24 to 32 alkylene oxide repeat units. In other methods, the fuel additives herein (if including alkoxylated alcohols) can also have about 8% or less (in other methods, about 6% or less, and in still other methods, about 4% or less) of C20 or higher alkoxylated alcohols and / or about 4 wt% or less (or in other methods about 2 wt% or less, and in still other methods, about 1 wt% or less) of C14 or lower alkoxylated alcohols.

[0084] Aryl- or hydrocarbyl-capped poly(alkylene oxide) alcohols can be produced by adding a lower alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to a desired hydroxy compound R-OH (i.e., the starting alcohol) under polymerization conditions, where R is an aryl or hydrocarbyl group having 5 to 30 carbons or other chain lengths as described above, and which caps the poly(alkylene oxide) chain. The alkoxylated alcohols can be prepared from any starting alcohol that provides the desired polyol distribution. By one method, the alkoxylated alcohols can be prepared by reacting a saturated straight-chain or branched-chain alcohol of a desired hydrocarbon size with a selected alkylene oxide and a bimetallic or basic catalyst. In one method, the alkoxylated alcohol can be a nonylphenol alkoxylated alcohol, such as nonylphenol propoxylated alcohol.

[0085] In other methods, in the polymerization reaction, a single type of alkylene oxide can be employed, such as propylene oxide, in which case the product is a homopolymer, such as poly(alkylene oxide) propanol. However, copolymers are also suitable, and random or block copolymers are readily prepared by contacting a hydroxy-containing compound with a mixture of alkylene oxides, such as a mixture of ethylene oxide, propylene oxide, and / or butylene oxide. Random polymers are more easily prepared when the reactivities of the oxides are relatively equal. In some cases, when ethylene oxide is copolymerized with other oxides, the higher reaction rate of ethylene oxide makes it difficult to prepare random copolymers. In either case, block copolymers can be prepared. Block copolymers are prepared by contacting a hydroxy-containing compound with a first alkylene oxide under polymerization conditions and then, in any order or repeatedly, with other alkylene oxides. In one example, a particular block copolymer can be represented by a polymer prepared by polymerizing propylene oxide on a suitable monohydroxy compound to form a poly(propylene oxide) alcohol and then polymerizing butylene oxide on the poly(alkylene oxide) alcohol.

[0086] The fuel additive or fuel of the present disclosure (when containing alkoxylated alcohols) may contain from about 5 wt% to about 30 wt% of alkoxylated alcohols, from about 8 wt% to about 20 wt% of alkoxylated alcohols, or from about 10 wt% to about 15 wt% of alkoxylated alcohols (based on the active alkoxylated alcohols in the fuel additive). When blended into a gasoline fuel, the fuel may contain from about 2 ppmw to about 150 ppmw of active alkoxylated alcohols, from about 5 ppmw to about 150 ppmw, from about 8 ppmw to about 50 ppmw, or from about 15 ppmw to about 40 ppmw of alkoxylated alcohols in the fuel.

[0087] In other methods, the fuel additive package or its fuel also has a specific weight ratio of alkoxylated alcohol to Mannich detergent of about 1.0 or less (i.e., about 1.0:1 or less), about 0.8 or less (i.e., 0.8:1 or less), about 0.6 or less, about 0.5 or less, about 0.4 or less, or about 0.3 or less, and about 0.1 or greater (i.e., 0.1:1 or greater), about 0.2 or greater, or about 0.3 or greater.

[0088] Fuel additive :

[0089] When formulating the fuel compositions of the present application, the above additives (at least containing one or more Mannich detergents and one or more Mannich-based quaternary ammonium salt detergents) can be used in an amount sufficient to reduce or inhibit the formation of deposits in the combustion chambers of the fuel system, engine, and / or crankcase and / or in the fuel injectors and in in-cylinder direct injection engines and / or port fuel injection engines. Such additives can also be provided in an amount to improve injector performance as described herein. In some aspects, the fuel additive or fuel additive package of the present disclosure may at least contain the above Mannich detergents, Mannich-based quaternary ammonium salt detergents, and optionally alkoxylated alcohols. The fuel additives of the present disclosure may also contain other optional additives according to the needs of specific applications, and may contain one or more of demulsifiers, corrosion inhibitors, anti-wear additives, antioxidants, metal deactivators, antistatic additives, defoggers, anti-knock additives, lubricity additives, and / or combustion promoters as needed.

[0090] In some methods or embodiments, the fuel additives or additive packages herein may comprise from about 20 wt% to about 60 wt% of one or more Mannich detergent additives (preferably, from about 25 wt% to about 50 wt%, most preferably, from about 25 wt% to about 40 wt%) and from about 1 wt% to about 50 wt% of one or more Mannich-based quaternary ammonium salt detergent additives (preferably, from about 3 wt% to about 10 wt%, most preferably, from about 4 wt% to about 8 wt%). In other methods, the fuel additive or additive package may further comprise from about 5 wt% to about 30 wt% of an alkoxylated alcohol (preferably, from about 10 wt% to about 25 wt%, most preferably, from about 12 wt% to about 20 wt%). Other ranges of Mannich detergent additives, Mannich-based quaternary ammonium salt detergents, and optionally alkoxylated alcohols may also be used for the fuel additives, additive packages, or fuels as described hereinabove.

[0091] In other methods, the gasoline fuel composition may comprise from about 40 ppmw to about 750 ppmw of the fuel additive or additive package herein, in other methods, from about 60 ppmw to about 380 ppmw, or from about 135 ppmw to about 310 ppmw of the above fuel additive package, and which provides to the fuel from about 15 ppmw to about 300 ppmw of Mannich detergent and from about 1 ppmw to about 200 ppmw of Mannich-based quaternary ammonium salt detergent (or other ranges as described above). In other embodiments, the fuel may further comprise from about 5 ppmw to about 150 ppmw of an optional alkoxylated alcohol (or other ranges as described above). It should also be understood that any endpoints between the ranges described above are also suitable range amounts depending on the needs of a particular application. The amounts above reflect the additives on an active ingredient basis, which means that the above additives do not include (i) the weight of unreacted components associated with and remaining in the product as produced and used, and (ii) the weight of any (one or more) solvents (if present) used in its manufacture during or after product formation.

[0092] In other methods and as discussed above, the fuel additive package or its fuel also has a specific weight ratio of alkoxylated alcohol to one or more Mannich detergents of about 1.0 or less (i.e., about 1.0:1 or less), about 0.8 or less (i.e., 0.8:1 or less), about 0.6 or less, about 0.5 or less, about 0.4 or less, or about 0.3 or less, and about 0.1 or greater (i.e., 0.1:1 or greater), about 0.2 or greater, or about 0.3 or greater.

[0093] In other methods, the fuel additive package or its fuel may also have a weight ratio of one or more Mannich detergents to one or more Mannich-based quaternary ammonium salt detergents of from about 1:1 to about 6:1, or from about 1:1 to about 5.5:1, or from about 1:1 to about 3:1 (wherein the weight ratio is of active Mannich detergent to active Mannich-based quaternary ammonium salt detergent). As shown in the examples below, such weight ratios achieve a surprising synergism of detergent additives in both FPI and GDI engine performance.

[0094] Other additives

[0095] One or more optional compounds may be present in the fuel compositions of the disclosed embodiments. For example, the fuel may contain conventional amounts of cetane improvers, octane improvers, corrosion inhibitors, cold flow improvers (CFPP additives), pour point depressants, solvents, demulsifiers, lubricity additives, friction modifiers, amine stabilizers, combustion improvers, detergents, dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, marker dyes, organic nitrate ignition promoters, cyclic tricarbonyl manganese compounds, carrier fluids, etc. In certain aspects, based on the total weight of the additive concentrate, the compositions described herein may contain about 10 wt% or less, or in other aspects, about 5 wt% or less of one or more of the above optional additives. Similarly, the fuel may contain suitable amounts of conventional fuel blend components such as methanol, ethanol, dialkyl ethers, 2-ethylhexanol, etc.

[0096] In certain aspects of the disclosed embodiments, organic nitrate ignition promoters may be used, which include aliphatic or cycloaliphatic nitrates, wherein the aliphatic or cycloaliphatic group is saturated and contains up to about 12 carbons. Examples of organic nitrate ignition promoters that may be used are methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-pentyl nitrate, 3-pentyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, cyclododecyl nitrate, 2-ethoxyethyl nitrate, 2-(2-ethoxyethoxy)ethyl nitrate, tetrahydrofuran nitrate, etc. Mixtures of such materials may also be used.

[0097] Examples of optional metal deactivators suitable for the compositions of the present application are disclosed in U.S. Patent No. 4,482,357, the disclosure of which is incorporated herein by reference in its entirety. Such metal deactivators include, for example, salicylidene-o-aminophenol, disalicylideneethylenediamine, disalicylidenepropylenediamine, and N,N'-disalicylidene-1,2-diaminopropane.

[0098] Suitable optional cyclic tricarbonyl manganese compounds that can be employed in the compositions of the present application include, for example, cyclopentadienyl tricarbonyl manganese, methylcyclopentadienyl tricarbonyl manganese, indenyl tricarbonyl manganese, and ethylcyclopentadienyl tricarbonyl manganese. Other examples of suitable cyclic tricarbonyl manganese compounds are disclosed in U.S. Patent No. 5,575,823 and U.S. Patent No. 3,015,668, the disclosures of both of which are incorporated herein by reference in their entireties.

[0099] Other commercially available detergents can be used in combination with the reaction products described herein. Such detergents include, but are not limited to, succinimides, Mannich base detergents, PIB amines, quaternary ammonium detergents, diamino triazole detergents, as generally described in U.S. Patent Application Serial No. 13 / 450,638, and reaction products of hydrocarbon-substituted dicarboxylic acids or acid anhydrides with aminoguanidine, wherein the reaction product has less than 1 equivalent of triazole groups per molecule, as generally described in U.S. Patent Application Serial Nos. 13 / 240,233 and 13 / 454,697.

[0100] The additives of the present application and optional additives for formulating the fuels of the present invention can be blended into the base fuel either individually or in various sub-combinations. In certain embodiments, the additive components of the present application can be simultaneously blended into the fuel using an additive concentrate, as this takes advantage of the compatibility and convenience provided by the combination of the components when in the form of an additive concentrate. In addition, using a concentrate can reduce blending time and the likelihood of blending errors.

[0101] Fuel

[0102] The fuel of the present application is applicable to operate diesel engines, jet engines or gasoline engines, preferably spark ignition engines or gasoline engines. The engines can include stationary engines (e.g., engines for power generation devices, pumping stations, etc.) and mobile engines (such as engines used as prime movers for automobiles, trucks, road leveling equipment, military vehicles, etc.). For example, the fuel can include any and all middle distillate fuels, diesel fuels, bio-renewable fuels, biodiesel fuels, fatty acid alkyl esters, gas to liquid (GTL) fuels, gasoline, jet fuels, alcohols, ethers, kerosene, low sulfur fuels, synthetic fuels such as Fischer-Tropsch fuels, liquefied petroleum gas, marine fuels, coal to liquid (CTL) fuels, biomass to liquid (BTL) fuels, high asphaltene fuels, fuels derived from coal (natural, clean and petroleum coke), genetically engineered biofuels and crops and their extracts and natural gas. Preferably, the additives herein are used in spark ignition fuels or gasoline. As used herein, "bio-renewable fuel" is understood to mean any fuel derived from resources other than petroleum. Such resources include, but are not limited to, grains, corn, soybeans and other crops; grasses such as switchgrass, miscanthus and hybrid grasses; algae, seaweed, vegetable oils; natural fats; and mixtures thereof. In one aspect, the bio-renewable fuel can contain monohydric alcohols, such as those containing from 1 to about 5 carbon atoms. Non-limiting examples of suitable monohydric alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, tert-butanol, pentanol and isopentanol. Preferred fuels include diesel fuel.

[0103] Accordingly, aspects of the present application relate to methods or uses of the fuel additive package for controlling or reducing fuel injector deposits, controlling or reducing intake valve deposits, controlling or reducing combustion chamber deposits, and / or controlling or reducing intake valve sticking in one (preferably both) of port fuel injection engines and gasoline direct injection engines. In some methods, the fuel additives and fuels herein are configured to reduce deposits when injected from an injector as droplets of from about 10 microns to about 30 microns, when injected from an injector as droplets of from about 120 microns to about 200 microns, or both. Thus, the fuel additives and fuels herein surprisingly provide improved engine performance as defined herein in both port fuel injection engines (PFI) and gasoline direct injection engines (GDI). In certain aspects, the method may further include mixing at least one of the optional additional components described above into the fuel. The improved engine performance can be evaluated according to the test procedure of ASTM D6201 or by the methods presented in the following two SAE publications: Smith, S. and Imoehl, W., “Measurement and Control of Fuel Injector Deposits in Direct Injection Gasoline Vehicles,” SAE Technical Paper 2013-01-2616, 2013, doi:10.4271 / 2013-01-2616; and / or Shanahan, C., Smith, S. and / or Sears, B., “A General Method for Fouling Injectors in Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance,” SAE Int. J. Fuels Lubr. 10(3):2017, doi:10.4271 / 2017-01-2298, which are incorporated herein by reference. The intake valve sticking can be evaluated using the test procedure in Southwest Research Institute (SWRI, San Antonio Texas) or a similar testing agency.

[0104] As used herein, the terms "hydrocarbyl substituent" or "hydrocarbyl group" are used in their ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly connected to the remainder of the molecule and predominantly having hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbyl substituents and substituted hydrocarbyl substituents containing one or more of a halogen group, a hydroxy group, an alkoxy group, a mercapto group, a nitro group, a nitroso group, an amino group, a pyridyl group, a furyl group, an imidazolyl group, oxygen, and nitrogen, and wherein there are no more than two non-hydrocarbyl substituents per ten carbon atoms in the hydrocarbyl group.

[0105] As used herein, unless otherwise expressly stated, the term "percent by weight" or "wt%" means the percentage by weight of the component in the total composition. Unless otherwise indicated, all percentages herein are weight percentages.

[0106] As used herein, the term "alkyl" refers to a straight-chain, branched-chain, cyclic, and / or substituted saturated chain moiety of from about 1 to about 200 carbon atoms. As used herein, the term "alkenyl" refers to a straight-chain, branched-chain, cyclic, and / or substituted unsaturated chain moiety of from about 3 to about 30 carbon atoms. As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds, which may include alkyl, alkenyl, alkylaryl, amino, hydroxy, alkoxy, halogen substituents, and / or heteroatoms including but not limited to nitrogen and oxygen.

[0107] As used herein, the molecular weight is determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having an Mp of about 162 to about 14,000 as a calibration reference). The molecular weight (Mn) of any embodiment herein can be measured using an instrument such as a gel permeation chromatography (GPC) instrument obtained from Waters, and the data can be processed using software such as Waters Empower software. The GPC instrument can be equipped with a Waters separation module and a Waters refractive index detector (or similar optional equipment). The GPC operating conditions can include a guard column, 4 Agilent PLgel columns (length is 300 × 7.5 mm; particle size is 5 μ, and the pore size range is ), the column temperature is about 40 °C. Unstabilized HPLC grade tetrahydrofuran (THF) can be used as the solvent, and the flow rate is 0.38 mL / min. The GPC instrument can be calibrated with commercially available polystyrene (PS) standards having a narrow molecular weight distribution in the range of 500 g / mol to 380,000 g / mol. For samples with a mass less than 500 g / mol, the calibration curve can be extrapolated. The samples and PS standards can be dissolved in THF and prepared at a concentration of 0.1 wt% to 0.5 wt% and used without filtration. GPC measurements are also described in US 5,266,223, which is incorporated herein by reference. The GPC method also provides molecular weight distribution information; see, for example, W.W. Yau, J.J. Kirkland, and D.D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is also incorporated herein by reference.

[0108] As used herein and unless the context otherwise indicates, a large amount means greater than 50 wt% (greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, or greater than 90 wt%), and a small amount means less than 50 wt% (less than 40 wt%, less than 30 wt%, less than 20 wt%, or less than 10 wt%).

[0109] It should be understood that throughout this disclosure, the terms "comprising", "including", "containing", etc. are considered to be open-ended and include any element, step, or component not expressly listed. The phrase "consisting essentially of" means including any expressly listed element, step, or component and any additional element, step, or component that does not materially affect the basic and novel aspects of the invention. This disclosure also contemplates that any composition described using the terms "comprising", "including", "containing" is also to be construed as including the disclosure of the same composition "consisting essentially of its specifically listed components" or "consisting of its specifically listed components".

[0110] Example

[0111] The following examples are illustrative of the exemplary embodiments of the present disclosure. In these examples as well as elsewhere in this application, all ratios, parts, and percentages are by weight unless otherwise indicated. These examples are presented for illustrative purposes only and are not intended to limit the scope of the invention disclosed herein. The specifications of the base fuels A, B, and C used in the examples are shown in Table 1 below.

[0112] Table 1: Fuel specifications 。

[0113]

[0114]

[0115] Example 1 :

[0116] The Mannich quaternary ammonium salt detergent additive is prepared as follows: An 80 wt% solution (in Aromatic 100 solvent) of a commercial sample of a Mannich fuel detergent made from polyisobutene (1000 MW) cresol, DMAPA, and formaldehyde (166.18 g, 150 mmol) was measured into a 500 ml round-bottom reaction flask equipped with a nitrogen port and a condenser. The main structure of this detergent is believed to be a compound having the following structure as shown below.

[0117]

[0118] Dimethyl oxalate (18.39 g, 156 mmol) was added to the solution. The mixture was heated to 125 °C and held for 3 hours. During the heating period, the mixture was stirred under a nitrogen atmosphere. At the end of the heating period, Aromatic 150 (80 g) was added to bring the total solvent concentration to 40 wt%. The 13 13C NMR spectrum of the product indicated that the quaternization of the tertiary amine had been completed.

[0119] Example 2

[0120] The inventive fuel additive packages and comparative fuel additive packages of Table 2 below were prepared to evaluate intake valve deposits. The Mannich detergents used in this example were prepared from highly reactive polyisobutene cresol, dimethylaminopropylamine, and formaldehyde according to known methods (see, for example, US6,800,103, which is incorporated herein by reference), the propoxylated alcohol was a blend of commercially available C16-C18 propoxylated alcohols, and the Mannich quaternary ammonium salt was the additive of Example 1.

[0121] Table 2

[0122]

[0123] Each of the additives in Table 2 above was blended into Base Fuel A. Then, the intake valve deposits of the base fuel without additives and the inventive fuels and comparative fuels were evaluated in a Ford 2.3L engine according to ASTM D6201. The results are provided in Table 3 below.

[0124] Table 3

[0125]

[0126] Example 4

[0127] In the context of GDI engines, a series of tests were conducted to evaluate the effect of additive packages on fuel injector deposits in gasoline direct injection (GDI) engines such as the Kia Optima engine or the General Motors LHU engine. All tests were conducted with a consistent base fuel during the contamination (DU), clean (CU), and / or keep clean (KC) phases of the respective tests. The additive packages in Table 4 below were tested to evaluate the ability of each fuel additive to improve injector performance by reducing injector deposits in GDI engines. The results are shown in Table 5.

[0128] Table 4: Fuel additives

[0129]

[0130] * Mannich detergent obtained from highly reactive polyisobutylene cresol, dibutylamine, and formaldehyde.

[0131] The DU level of base fuel B was studied by indirectly measuring injector fouling on a direct injection GM LHU engine, such as by pulse width or long-term fuel trim (LTFT), according to the RIFT method described in Smith, S. and Imoehl, W., “Measurement and Control of Fuel Injector Deposits in Direct Injection Gasoline Vehicles,” SAE Technical Paper 2013-01-2616, 2013, doi:10.4271 / 2013-01-2616; and / or Shanahan, C., Smith, S. and / or Sears, B., “A General Method for Fouling Injectors in Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance,” SAE Int. J. Fuels Lubr. 10(3):2017, doi:10.4271 / 2017-01-2298, which are incorporated herein by reference.

[0132] To accelerate the DU phase of the base fuel, a combination of di-tert-butyl disulfide (DTBDS 406 ppmw) and tert-butyl hydroperoxide (TBHP, 286 ppmw) was added to the base fuel, and the DU was accelerated to provide fouling in the range of 5% to 12%. The fouling percentage was calculated as follows:

[0133]

[0134] A GDI cleaning (CU) deposit test was conducted to demonstrate the removal of deposits that had formed in the fuel injectors during the contamination (DU) phase. The additive package of Table 6 was blended into the base fuel B for DU. The test procedure consisted of a 114-hour cycle at 2000 rpm and 100 Nm of torque, continuously monitoring the injection pulse width to maintain the stoichiometric air / fuel ratio on a GM LHU engine. After 66 hours of test operation, the fuel was changed to an additive formulation designed to have a cleaning effect. After completion of the 114-hour cycle, the percentage increase and subsequent decrease in the injector pulse width was a parameter used to evaluate the fouling or cleaning effect of the fuel candidate. CU was calculated according to the following equation:

[0135]

[0136] Table 5: GDI Cleaning in Kia Optima Engine

[0137]

[0138] *GM LHU engine

[0139] As shown in Tables 4 and 5, with respect to the comparative examples using only Mannich detergents or Mannich-based quaternary salt detergents alone, Sample 2 of the present invention using both Mannich detergent additives and Mannich-based quaternary ammonium additives at a ratio of 5.2:1 exhibited improved injector cleaning. Given that a fuel additive containing only a Mannich-based quaternary salt detergent (e.g., Comparative Example 3) had no cleaning performance in a GDI engine (but rather continued the contamination phase), Sample 2 of the present invention containing both Mannich detergents and Mannich-based quaternary salt detergents showed an unexpected synergistic effect in terms of performance. That is, considering that a Mannich-based quaternary salt detergent alone did not provide cleaning performance (but rather continued the DU), it was not expected that the cleaning performance of both Mannich detergents and Mannich-based quaternary salts would be superior to that of Comparative Sample 4 containing only Mannich detergents.

[0140] It should be noted that, unless explicitly and affirmatively limited to one referent, the singular forms "a" and "the" as used in this specification and the appended claims include plural referents. Thus, for example, reference to "an antioxidant" includes two or more different antioxidants. The term "comprising" and its grammatical variants as used herein are intended to be non-limiting, such that recitation of items in a list does not preclude other like items that may be substituted or added to the listed items.

[0141] For this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages, or proportions, as well as other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0142] It should be understood that each component, compound, substituent, or parameter disclosed herein is to be construed as being disclosed for use alone or in combination with one or more of each of the other components, compounds, substituents, or parameters disclosed herein.

[0143] It should be further understood that each range disclosed herein is to be construed as an express disclosure of every specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 is to be construed as an express disclosure of the values 1, 2, 3, and 4, and any range of such values.

[0144] It should be further understood that each lower limit of each range disclosed herein is to be construed as being disclosed in combination with each upper limit of each range and each specific value within each range for the same component, compound, substituent, or parameter disclosed herein. Accordingly, this disclosure is to be construed as an express disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is to say, it should be further understood that this disclosure also contemplates any range between the endpoint values within a broad range. Thus, a range of 1 to 4 also means ranges of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0145] In addition, the specific amounts / values of components, compounds, substituents or parameters disclosed in this specification or the embodiments should be construed as the disclosure of the lower or upper limit of a certain range, and thus can be combined with any other lower or upper limit or specific amount / value of the range of the same components, compounds, substituents or parameters disclosed elsewhere in this disclosure to form the range of that component, compound, substituent or parameter.

Claims

1. A fuel additive for a spark ignition engine, the fuel additive comprising: a detergent comprising one or more Mannich detergent additives and one or more Mannich-based quaternary ammonium salt detergent additives; wherein the one or more Mannich detergent additives include the reaction product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more amines; wherein the one or more Mannich-based quaternary ammonium salt detergent additives include (i) a Mannich reaction product or a derivative thereof having at least one tertiary amino group and prepared from a hydrocarbyl-substituted phenol, cresol or derivative thereof, an aldehyde and a hydrocarbyl amine or polyamine providing the tertiary amino group and reacted with (ii) a quaternizing agent selected from the group consisting of a carboxylic acid or polycarboxylic acid, an ester, an amide or a salt thereof or a halogen-substituted derivative thereof; and About 2 wt % to about 50 wt % of the detergent is the one or more Mannich-based quaternary ammonium salt detergent additives.

2. The fuel additive of claim 1, wherein about 2 wt % to about 20 wt % of the detergent is the one or more Mannich-based quaternary ammonium salt detergent additives; and / or wherein the one or more Mannich detergent additives have a structure of Formula I: Wherein R1 of Formula I is hydrogen or a C1 to C4 alkyl group, R2 of Formula I is a hydrocarbon group having a number average molecular weight of about 500 to about 3000, and preferably R2 of Formula I is a polyisobutylene group having a number average molecular weight of about 500 to about 1500, R3 of Formula I is a C1 to C4 alkylene or alkenyl group, and R4 and R5 of Formula I are independently hydrogen, a C1 to C12 alkyl group or a C1 to C4 alkylaminodi(C1-C12 alkyl) group.

3. The fuel additive of claim 2, wherein the detergent comprises two Mannich detergent additives, wherein a first Mannich detergent additive has a structure of Formula I, wherein R4 and R5 are each said C1 to C12 alkyl group, and a second Mannich detergent additive has a structure of Formula I, wherein R4 is hydrogen and R5 is a di(C1 to C4)alkylamino C1-C12 alkyl group; and / or wherein the first Mannich detergent additive has a structure of Formula Ia and the second Mannich detergent additive has a structure of Formula Ib: wherein each R1 is independently hydrogen or a C1 to C4 alkyl group, each R2 is independently a hydrocarbon group having a number average molecular weight of about 500 to about 3000, and R6 and R7 are independently C1 to C12 alkyl groups; and / or wherein the detergent comprises about 10 wt % to about 30 wt % of the first Mannich detergent additive and about 10 wt % to about 30 wt % of the second Mannich detergent additive; and / or wherein the weight ratio of the first Mannich detergent additive to the second Mannich detergent additive is about 1:1 to about 2:

1.

4. The fuel additive of claim 1, wherein the one or more Mannich-based quaternary ammonium salt detergent additives have the structure of Formula II in R8 is a hydrocarbon group, wherein the number average molecular weight of the hydrocarbon group is from about 200 to about 5,000; R9 is hydrogen or a C1-C6 alkyl group; R 10 is hydrogen or is 11 A -C(O)- group or a -CH2- group that together with the nitrogen atom closest to the aromatic ring forms a ring structure; R 11 is hydrogen, C1-C6 alkyl, -(CH2) a -NR5R6, -(CH2) a -aryl (R1)(R2)(OR3) or 10 one of a -C(O)- group or a -CH2- group (each of R5 and R6 is independently a C1 to C12 alkyl group) which together form a ring structure with the nitrogen atom closest to the aromatic ring; R 12 is a C1-C6 alkyl group, or with Y Together they form a C1-C6 alkyl-substituted -C(O)O ; R 13 and R 14 are independently C1-C6 alkyl; a is an integer from 1 to 10, b is an integer selected from 0 or 1, and c is an integer from 0 to 10; X is oxygen or nitrogen; and Y For a structure R 15 C(O)O Anionic groups, where R 15 One of the following: (i) with R 12 Together they are a C1-C6 alkyl group or (ii) a C1-C6 alkyl, aryl, C1-C4 alkylene-C(O)O-R2 or -C(O)O-R2 group (R2 is a C1 to C6 alkyl group).

5. The fuel additive of claim 4, wherein R8 of Formula II is a hydrocarbon group derived from a polyisobutylene polymer or oligomer, having a number average molecular weight of about 500 to about 1,500, R9 of Formula II is a hydrogen or methyl group, and R 10 and R 11 are each hydrogen; a is an integer from 1 to 4, and b and c are each 0; and / or wherein R 12 , R 13 and R 14 are each C1-C6 alkyl, and wherein Y For the structure R 15 C(O)O The anionic group, wherein R 15 It is a C1-C6 alkyl group, an aryl group, a C1-C4 alkylene group, a -C(O)O-R2 group, or a -C(O)O-R2 group.

6. The fuel additive of claim 1, further comprising an alkoxylated alcohol, and wherein the weight ratio of the alkoxylated alcohol to the one or more Mannich detergent additives is about 1.0 or less; and / or wherein the alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol or an alkyl phenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations thereof; and / or wherein the alkoxylated alcohol is a polyether having a structure of Formula VI: Wherein R6 of Formula VI is an aryl group or a linear, branched or cyclic aliphatic group having 5 to 50 carbons, R7 of Formula VI is a C1 to C4 alkyl group, and n is an integer from 5 to 100.

7. A gasoline fuel composition, comprising: a detergent comprising one or more Mannich detergent additives and one or more Mannich-based quaternary ammonium salt detergent additives; from about 15 ppmw to about 300 ppmw of the one or more Mannich detergent additives, wherein the Mannich detergent additive is the reaction product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes, and one or more amines; from about 1 ppmw to about 200 ppmw of the one or more Mannich-based quaternary ammonium salt detergent additives, wherein the Mannich-based quaternary ammonium salt detergent additive is (i) a Mannich reaction product or a derivative thereof having at least one tertiary amino group and prepared from a hydrocarbyl-substituted phenol, cresol or derivative thereof, an aldehyde and a hydrocarbyl amine or polyamine providing the tertiary amino group, and reacted with (ii) a quaternizing agent selected from the group consisting of a carboxylic acid or polycarboxylic acid, an ester, an amide or a salt thereof or a halogen-substituted derivative thereof; wherein about 2 wt % to about 50 wt % of the detergent is the one or more Mannich-based quaternary ammonium salt detergent additives; and From about 5 ppmw to about 150 ppmw of alkoxylated alcohol.

8. A method for reducing deposits in a gasoline engine, the method comprising: operating a gasoline engine with a fuel composition comprising a major amount of gasoline fuel and a minor amount of a fuel additive by injecting the gasoline fuel through one or more injectors; wherein the fuel additive comprises a detergent, the detergent comprising one or more Mannich detergent additives and one or more Mannich-based quaternary ammonium salt detergent additives; wherein the one or more Mannich detergent additives comprise the reaction product of a hydrocarbyl-substituted phenol or cresol, one or more aldehydes and one or more amines; wherein the Mannich-based quaternary ammonium salt detergent additive comprises (i) a Mannich reaction product or a derivative thereof having at least one tertiary amino group and prepared from a hydrocarbyl-substituted phenol, a cresol or a derivative thereof, an aldehyde and a hydrocarbyl amine or polyamine providing the tertiary amino group, and reacted with (ii) a quaternizing agent selected from the group consisting of a carboxylic acid or polycarboxylic acid, an ester, an amide or a salt thereof or a halogen-substituted derivative thereof; and wherein about 2 wt % Up to about 50% by weight of the detergent is the one or more Mannich-based quaternary ammonium salt detergent additives; and wherein the fuel additive reduces deposits in the gasoline engine.

9. The method of claim 8, wherein the fuel additive reduces deposits in a port fuel injection (PFI) engine, a direct injection (GDI) engine, or both; and / or wherein the reduced deposits are reduced injector deposits as measured by one of injector pulse width, injection duration, injector flow, or a combination thereof; and / or wherein the fuel additive reduces deposits when injected from an injector configured to inject droplets of about 10 microns to about 30 microns, about 120 microns to about 200 microns, or both.

10. The method of claim 8, wherein the one or more Mannich detergent additives have the structure of Formula I: wherein R1 is hydrogen or a C1 to C4 alkyl group, R2 is a hydrocarbon group having a number average molecular weight of about 500 to about 3000, and preferably R2 is a polyisobutylene group having a number average molecular weight of 1500 to 1500, R3 is a C1 to C4 alkylene or alkenyl group, and R4 and R5 are independently hydrogen, a C1 to C12 alkyl group or a di(C1 to C4)alkylamino C1-C12 alkyl group.

11. The method of claim 8, wherein the one or more Mannich-based quaternary ammonium salt detergent additives have the structure of Formula II in R8 is a hydrocarbon group, wherein the number average molecular weight of the hydrocarbon group is from about 200 to about 5,000; R9 is hydrogen or a C1-C6 alkyl group; R 10 is hydrogen or is 11 A -C(O)- group or a -CH2- group that together with the nitrogen atom closest to the aromatic ring forms a ring structure; R 11 is hydrogen, C1-C6 alkyl, -(CH2) a -NR5R6, -(CH2) a -aryl (R1)(R2)(OR3) or 10 one of a -C(O)- group or a -CH2- group (each of R5 and R6 is independently a C1 to C12 alkyl group) which together form a ring structure with the nitrogen atom closest to the aromatic ring; R 12 is a C1-C6 alkyl group, or with Y Together they form a C1-C6 alkyl-substituted -C(O)O ; R 13 and R 14 are independently C1-C6 alkyl; a is an integer from 1 to 10, b is an integer selected from 0 or 1, and c is an integer from 0 to 10; X is oxygen or nitrogen; and Y For a structure R 15 C(O)O Anionic groups, where R 15 One of the following: (i) with R 12 together are a C1-C6 alkyl group or (ii) a C1-C6 alkyl, aryl, C1-C4 alkylene -C(O)O-R2 or -C(O)O-R2 group (R2 is a C1 to C6 alkyl group).

12. The method of claim 11, wherein R8 is a hydrocarbyl group derived from a polyisobutylene polymer or oligomer, having a number average molecular weight of about 500 to about 1,500, R9 is hydrogen or a methyl group, and R 10 and R 11 are each hydrogen; a is an integer from 1 to 4, and b and c are each 0; and / or wherein R 12 , R 13 and R 14 are each C1-C6 alkyl, and wherein Y For the structure R 15 C(O)O The anionic group, wherein R 15 It is the C1-C6 alkyl, aryl, C1-C4 alkylene-C(O)O-R2 or -C(O)O-R2 group.

13. The method of claim 8, further comprising an alkoxylated alcohol, and wherein the weight ratio of the alkoxylated alcohol to the Mannich detergent is about 1.0 or less; and / or wherein the alkoxylated alcohol is a polyether prepared by reacting an alkyl alcohol or an alkyl phenol with an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, copolymers thereof, or combinations thereof; and / or wherein the alkoxylated alcohol is a polyether having a structure of Formula VI: Wherein R6 of formula III is an aryl group or a linear, branched or cyclic aliphatic group having 5 to 50 carbons, R7 of formula III is a C1 to C4 alkyl group, and n is an integer from 5 to 100.

14. The method of claim 8, wherein the fuel additive comprises from about 20 wt % to about 60 wt % of the Mannich detergent, from about 1 wt % to about 50 wt % of the one or more Mannich-based quaternary ammonium salt detergent additives, and from about 5 wt % to about 30 wt % of the alkoxylated alcohol.

15. The method of claim 8, wherein the detergent comprises two Mannich detergent additives, wherein a first Mannich detergent additive has a structure of Formula I, wherein R4 and R5 are each said C1 to C12 alkyl group, and a second Mannich detergent additive has a structure of Formula I, wherein R4 is hydrogen and R5 is a di(C1 to C4)alkylamino C1-C12 alkyl group; and / or wherein the first Mannich detergent additive has a structure of Formula Ia and the second Mannich detergent additive has a structure of Formula Ib: wherein each R1 is independently hydrogen or a C1 to C4 alkyl group, each R2 is independently a hydrocarbon group having a number average molecular weight of about 500 to about 3000, and R6 and R7 are independently C1 to C12 alkyl groups; and / or wherein the detergent comprises about 10 wt % to about 30 wt % of the first Mannich detergent additive and about 10 wt % to about 30 wt % of the second Mannich detergent additive; and / or wherein the weight ratio of the first Mannich detergent additive to the second Mannich detergent additive is about 1:1 to about 2:1.

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