Diesel detergents without low molecular weight losses

Abstract

The present invention relates to quaternary ammonium salt detergents and the use of such quaternary ammonium salt detergents in fuel compositions to reduce diesel injector deposits and to remove or clean existing deposits on diesel injectors. The present invention also relates to diesel detergents that do not have low molecular weight losses.

Description

[0001] This application is a divisional application of patent application No. 201380055170.3, filed on October 22, 2013, entitled "Diesel Cleaner Without Low Molecular Weight Loss". Technical Field

[0002] The compositions of the present invention relate to quaternary ammonium salt detergents and the use of such quaternary ammonium salt detergents in fuel compositions to reduce diesel injector deposits and to remove or clean existing deposits on diesel injectors. Background Technology

[0003] Liquid fuels contain components that can degrade and form deposits during engine operation. These deposits can lead to incomplete combustion of the fuel, resulting in higher emissions and poorer fuel economy. Fuel additives, such as detergents, are well-known additives in liquid fuels that help control or minimize deposit formation. Due to the dynamics and mechanics of continuous engine propulsion, fuel requirements must evolve to keep pace with these engine developments. For example, current engines have injector systems with smaller tolerances and operate at higher pressures to enhance fuel injection into the compression or combustion chamber. Deposit prevention and reduction in these new engines have become critical for optimal engine operation. The development of fuel additives, such as detergents, enables fuels to align with these engine developments. Therefore, detergents are needed that can provide acceptable performance in liquid fuels to promote optimal operation of current engines.

[0004] US 5,000,792 discloses a polyesteramine detergent that can be obtained by reacting 2 parts of polyhydroxycarboxylic acid with 1 part of dialkyltriamine.

[0005] US 4,171,959 discloses engine fuel compositions comprising quaternary ammonium salts containing succinimide. The quaternary ammonium salts have counterions of halides, sulfonates, or carboxylates.

[0006] US 4,338,206 and US 4,326,973 disclose fuel compositions comprising quaternary ammonium salts containing succinimide, wherein the ammonium ion is a heterocyclic aromatic (pyridine) group. ion).

[0007] US 4,108,858 discloses a compound containing 800-1400 Mw and pyridine. A fuel or lubricating oil composition of salted C2-C4 polyolefins.

[0008] US 5,254,138 discloses a fuel composition comprising the reaction product of polyalkyl succinic anhydride and polyaminohydroxyalkyl quaternary ammonium salt.

[0009] US 4,056,531 discloses lubricating oils or fuels comprising a quaternary ammonium salt of a hydrocarbon having a Mw of 350-3000 bonded to triethylenediamine. The counterion of the quaternary ammonium salt is selected from halides, phosphates, alkyl phosphates, dialkyl phosphates, borates, alkyl borates, nitrites, nitrates, carbonates, bicarbonates, alkoxides, and O,O-dialkyldithiophosphates.

[0010] US 4,248,719 discloses fuels or lubricants comprising quaternary ammonium salts of succinimide and monocarboxylic acid esters. US 4,248,719 does not teach, imply, or disclose the presence of low-sulfur fuels, fluidizers, etc. Example 1 teaches a polyisobutylene succinimide having DMAPA as an amine. The succinimide is then reacted with salicylate.

[0011] US 4,253,980 and US 4,306,070 disclose fuel compositions comprising quaternary ammonium salts containing ester-lactones.

[0012] US 3,778,371 discloses a lubricating oil or fuel comprising a quaternary ammonium salt of a hydrocarbon having a Mw of 350-3000; and the remaining groups on the quaternary nitrogen are selected from C1-C1. 20 Alkyl, C2-C8 hydroxyalkyl, C2-C 20 Alkenyl or cyclic groups.

[0013] US 2011 / 0302828 by Fang et al., published on December 15, 2011, discloses a diesel fuel composition comprising a diesel fuel additive having a number average molecular weight of 500-10,000, wherein less than 25% by weight of the additive has a molecular weight of 400 or less.

[0014] Therefore, this invention promotes optimal engine operation by reducing, minimizing and controlling deposit formation, namely improved fuel economy, better vehicle driving performance, reduced emissions and less engine maintenance. Summary of the Invention

[0015] The present invention further provides a method for refueling an internal combustion engine, the method comprising:

[0016] A. Supplying the following to the engine:

[0017] I. Fuels that are liquid at room temperature; and

[0018] II. Quaternary ammonium salts of reaction products containing the following components:

[0019] (a) A compound comprising (i) at least one tertiary amino group and (ii) a hydrocarbon substituent having a number average molecular weight of about 100 to about 500; and

[0020] (b) A quaternizing agent suitable for converting the tertiary amino group of (a)(i) into a quaternary nitrogen group.

[0021] The quaternizing agent is selected from dialkyl sulfate esters, benzyl halides, hydrocarbon-substituted carbonates; hydrocarbon epoxides, hydrocarbon epoxides combined with acids, or mixtures thereof.

[0022] The present invention also provides compositions comprising quaternary ammonium salts, wherein the quaternary ammonium salts comprise reaction products of the following components:

[0023] (a) A compound comprising (i) at least one tertiary amino group and (ii) a hydrocarbon substituent having a number average molecular weight of about 100 to about 500; and

[0024] (b) A quaternizing agent suitable for converting the tertiary amino group of (a)(i) into a quaternary nitrogen.

[0025] The above composition may further comprise a quaternary ammonium salt, wherein the quaternary ammonium salt comprises the reaction product of the following components:

[0026] a) A compound comprising (i) at least one tertiary amino group, and (ii) a hydrocarbon substituent derived from a hydrocarbon having a number average molecular weight of about 500 to about 5000; and

[0027] b) A quaternizing agent suitable for converting the tertiary amino group of compound (a) into a quaternary nitrogen group. Detailed Implementation

[0028] The preferred features and implementation schemes are described below in a non-limiting manner.

[0029] This invention relates to quaternary ammonium salts, fuel compositions comprising said quaternary ammonium salts, and methods for operating internal combustion engines with said fuel compositions. The compositions and methods of this invention minimize, reduce, and control deposit formation in engines, which reduces fuel consumption, improves driving performance and vehicle maintenance, and reduces emissions, resulting in optimal engine operation.

[0030] fuel

[0031] The compositions of this invention may comprise a fuel that is liquid at room temperature and is used to fuel an engine. This fuel is typically liquid under ambient conditions, such as room temperature (20-30°C). The fuel may be a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof. Hydrocarbon fuels may be petroleum fractions, including gasoline as defined in ASTM specification D4814 or diesel fuel as defined in ASTM specification D975. In one embodiment of the invention, the fuel is gasoline; in other embodiments, the fuel is leaded or unleaded gasoline. In another embodiment of the invention, the fuel is diesel fuel. Hydrocarbon fuels may be hydrocarbons prepared by natural gas synthesis methods, including, for example, hydrocarbons prepared by methods such as the Fischer-Tropsch process. Non-hydrocarbon fuels may be oxygen-containing compositions, commonly referred to as oxycarbons, including alcohols, ethers, ketones, carboxylic acid esters, nitroalkanes, or mixtures thereof. Non-hydrocarbon fuels may include, for example, methanol, ethanol, methyl tert-butyl ether, methyl ethyl ketone, transesterified oils and / or fats from plants and animals such as rapeseed methyl ester and soybean methyl ester, and nitromethane. Mixtures of hydrocarbon and non-hydrocarbon fuels may include, for example, gasoline and methanol and / or ethanol, diesel fuel and ethanol, and diesel fuel and transesterified vegetable oils such as rapeseed methyl ester. In one embodiment of the invention, the liquid fuel is an emulsion of water in a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof. In several embodiments of the invention, the fuel may have a sulfur content of 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less based on weight. In another embodiment, the fuel may have a sulfur content of 1-100 ppm based on weight. In one embodiment, the fuel contains about 0 ppm to about 1000 ppm, about 0 to about 500 ppm, about 0 to about 100 ppm, about 0 to about 50 ppm, about 0 to about 25 ppm, about 0 to about 10 ppm, or about 0-5 ppm of alkali metals, alkaline earth metals, transition metals, or mixtures thereof. In another embodiment, the fuel contains 1-10 ppm by weight of alkali metals, alkaline earth metals, transition metals, or mixtures thereof. Fuels containing alkali metals, alkaline earth metals, transition metals, or mixtures thereof are known in the art to have a greater tendency to form deposits and thus scale or clog common rail injectors. The fuels of the present invention are present in the fuel composition in a major amount typically greater than 50% by weight, and in other embodiments, in greater than 90% by weight, greater than 95% by weight, greater than 99.5% by weight, or greater than 99.8% by weight.

[0032] Quaternary ammonium salts

[0033] The quaternary ammonium salts of the present invention comprise reaction products of the following components: (i) a compound containing at least one tertiary amino group and a hydrocarbon substituent derived from a hydrocarbon having a number average molecular weight of about 100 to about 500, or 100 to about 450, 150 to about 400, or 200 to about 350; and (ii) a quaternizing agent suitable for converting the tertiary amino group of compound (i) into a quaternary nitrogen.

[0034] The hydrocarbon substituents having a number average molecular weight of about 100 to about 500, or 100 to about 450, 150 to about 400, or 200 to about 350, can be, for example, polyolefins, polyalkylene compounds, or esters or polyesters. Thus, an example quaternary ammonium salt containing a hydrocarbon substituent can include, for example, a reaction product comprising: (i) at least one compound, said compound comprising: (a) a condensation product of a hydrocarbon-substituted acylating agent and a compound having an oxygen or nitrogen atom capable of condensing with the acylating agent, wherein the condensation product has at least one tertiary amino group; (b) a polyalkylene-substituted amine having at least one tertiary amino group; and (c) a polyester comprising a reaction product of an aliphatic carboxylic acid containing at least one hydroxyl group and a compound having an oxygen or nitrogen atom capable of condensing with said acid, wherein said compound contains a tertiary amino group; and (ii) a quaternizing agent adapted to convert the tertiary amino compound of (i) into a quaternary nitrogen compound.

[0035] The quaternary ammonium salt of the present invention further includes the reaction product of the following components: (i) a compound containing at least one tertiary amino group; and (ii) a quaternizing agent suitable for converting the tertiary amino group of compound (i) into a quaternary nitrogen.

[0036] Example quaternary ammonium salts may include reaction products of, for example, the following components: (i) at least one compound, said compound may include: (d) a Mannich reaction product having at least one tertiary amino group, wherein the Mannich reaction product is derived from a hydrocarbon-substituted phenol, aldehyde, or amine; (e) a non-quaternized amide and / or ester detergent having tertiary amine functionality; and (ii) a quaternizing agent adapted to convert the tertiary amino group of compound (i) into a quaternary nitrogen.

[0037] Quaternizing agents may include dialkyl sulfates, benzyl halides, alkyl-substituted carbonates and alkyl epoxides, any of which may be used in combination with an acid.

[0038] The compounds of components (i)(a) to (i)(e) described in more detail below contain at least one tertiary amino group and include compounds that can be alkylated to contain at least one tertiary amino group after an alkylation step.

[0039] Examples of quaternary ammonium salts and methods for their preparation are described in U.S. Patents: 4,253,980; 3,778,371; 4,171,959; 4,326,973; 4,338,206; and 5,254,138.

[0040] Quaternary ammonium salts can be prepared in the presence of a solvent, which may or may not be removed upon completion of the reaction. Suitable solvents include, but are not limited to, diluent oils, petroleum naphtha, and certain alcohols. In one embodiment, these alcohols contain at least 2 carbon atoms; in other embodiments, at least 4, at least 6, or at least 8 carbon atoms. In another embodiment, the solvent of the present invention contains 2-20 carbon atoms, 4-16 carbon atoms, 6-12 carbon atoms, 8-10 carbon atoms, or exactly 8 carbon atoms. These alcohols typically have a 2-(C) group. 1-4 The alkyl substituent is any isomer of methyl, ethyl, propyl, or butyl. Examples of suitable alcohols include 2-propylheptanol, 2-methyldecanol, 2-ethylpentanol, 2-ethylhexanol, 2-ethylnonanol, 2-propylheptanol, 2-butylheptanol, 2-butyloctanol, isooctanol, dodecyl alcohol, cyclohexanol, methanol, ethanol, propan-1-ol, 2-methylpropan-2-ol, 2-methylpropan-1-ol, butan-1-ol, butan-2-ol, pentanol, and their isomers, and mixtures thereof. In one embodiment, the solvent of the present invention is 2-ethylhexanol, 2-ethylnonanol, 2-methylheptanol, or a combination thereof. In one embodiment, the solvent of the present invention is 2-ethylhexanol.

[0041] This document describes various embodiments of suitable quaternary ammonium salts, and the present invention is intended to use any one of them or a combination thereof.

[0042] Succinimide Quaternary Ammonium Salt

[0043] In one embodiment, the quaternary salt detergent comprises a reaction product of the following components: (i)(a) a hydrocarbon-substituted acylating agent and a condensation product of a compound having an oxygen or nitrogen atom capable of condensing with the acylating agent, wherein the condensation product has at least one tertiary amino group; and (ii) a quaternizing agent adapted to convert the tertiary amino group of compound (i) into a quaternary nitrogen.

[0044] The hydrocarbon-substituted acylated agents used in this invention include short-chain hydrocarbons, typically polyolefins, and reaction products with monounsaturated carboxylic acids or their derivatives.

[0045] Suitable monounsaturated carboxylic acids or their derivatives include: (i) α,β-monounsaturated C4-C 10 Dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid; (ii) derivatives of (i) such as anhydrides of (i) or mono- or diesters derived from C1-C5 alcohols; (iii) α,β-monounsaturated C3-C 10 Monocarboxylic acids such as acrylic acid and methacrylic acid; or derivatives of (iv)(iii), such as C1-C5 alcohol derivatives of (iii).

[0046] The short-chain hydrocarbons used to prepare alkyl-substituted acylated agents may have a number average molecular weight of about 100 to about 500, or 100 to about 450, 150 to about 400, or 200 to about 350. Suitable hydrocarbons include any compound containing an olefin bond represented by general formula I shown herein:

[0047] (R 1 (R) 2 C = C(R) 3 )(CH(R 4 (R) 5 )) (I)

[0048] Where R 1 R 2 R 3 R 4 and R 5 Each is independently a hydrogen or hydrocarbon group. In some embodiments, R 3 R 4 Or R 5 At least one of them is a hydrocarbon group containing up to about 36 carbon atoms.

[0049] This can also be described as the reaction of these short-chain hydrocarbons of polyolefins or olefin polymers with the aforementioned monounsaturated carboxylic acids and derivatives to form hydrocarbon-substituted acylation agents for the preparation of the nitrogen-containing detergents of the present invention. Suitable olefin polymers include those comprising C2-C44 in predominant molar amounts. 20 Polymers of C2-C5 monoolefins, or C2-C5 monoolefins. These olefins include ethylene, propylene, butene, isobutylene, pentene, octene-1, or styrene. The polymer can be a homopolymer, such as polyisobutylene, and copolymers of two or more of these olefins. Suitable copolymers include copolymers of ethylene and propylene, butene and isobutylene, and propylene and isobutylene. Other suitable copolymers include those in which a minor molar percentage, such as 1-10 mol%, of the copolymer monomer is C4-C5. 18 Those copolymers containing dienes. These copolymers include copolymers of isobutylene and butadiene; and copolymers of ethylene, propylene and 1,4-hexadiene.

[0050] In one embodiment, at least one –R group of formula (I) shown above is derived from polybutene, i.e., a C4 olefin, including polymers of 1-butene, 2-butene, and isobutene. C4 polymers include polyisobutene. In another embodiment, at least one –R group of formula I is derived from an ethylene-α-olefin polymer, including ethylene-propylene-diene polymers. Examples of documents describing ethylene-α-olefin copolymers and ethylene-lower olefin-diene ternary polymers include U.S. Patents: 3,598,738; 4,026,809; 4,032,700; 4,137,185; 4,156,061; 4,320,019; 4,357,250; 4,658,078; 4,668,834; 4,937,299; and 5,324,800.

[0051] In another embodiment, the olefinic bonds of formula (I) are primarily vinylides represented by the following formula:

[0052]

[0053] Each R is a hydrocarbon group; in some embodiments, it can be:

[0054]

[0055] Each R represents a hydrocarbon group.

[0056] In one embodiment, the vinylidene content of formula (I) may comprise at least 30 mol% vinylidene, at least 50 mol% vinylidene, or at least 70 mol% vinylidene. Such materials and methods of preparation are described in U.S. Patents: 5,071,919; 5,137,978; 5,137,980; 5,286,823, 5,408,018, 6,562,913, 6,683,138, 7,037,999; and U.S. Patent Publications: 2004 / 0176552A1; 2005 / 0137363; and 2006 / 0079652A1. Such products are marketed under the trade name GLISSOPAL. TM By BASF, and under the trade name TPC 1105 TM and TPC 595 TM Purchased from Texas PetroChemical LP.

[0057] Methods for preparing hydrocarbon-substituted acylated agents by reacting a monounsaturated carboxylic acid reactant with a compound of formula (I) are well known in the art and disclosed in U.S. Patents: 3,361,673; 3,401,118; 3,087,436; 3,172,892; 3,272,746, 3,215,707; 3,231,587; 3,912,764; 4,110,349; 4,234,435; 6,077,909; and 6,165,235.

[0058] In another embodiment, the hydrocarbon-substituted acylated agent can be prepared by reacting a compound of formula (I) with at least one carboxylic acid reactant of formula (I):

[0059]

[0060] and

[0061]

[0062] Where R 6 R 8 and R 9 Each is independently an H or hydrocarbon group, R 7 It is a divalent alkylene group, and n is 0 or 1. Such compounds and their preparation methods are disclosed in U.S. Patents: 5,739,356; 5,777,142; 5,786,490; 5,856,524; 6,020,500; and 6,114,547.

[0063] In yet another embodiment, the alkyl-substituted acylated agent may be prepared by reacting any compound of formula (I) with any compound of formula (IV) or formula (V), wherein the reaction is carried out in the presence of at least one aldehyde or ketone. Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, hexanal, heptanal, octanal, benzaldehyde, and higher aldehydes. Other aldehydes such as dialdehydes, especially glyoxal, are useful, although monoaldehydes are generally preferred. In one embodiment, the aldehyde is formaldehyde, which may be provided in an aqueous solution commonly known as formaldehyde water, but more commonly in a polymeric form known as secondary formaldehyde. Secondary formaldehyde is considered a reactive equivalent and / or source of formaldehyde. Other reactive equivalents include hydrates or cyclic trimers. Suitable ketones include acetone, butanone, methyl ethyl ketone, and other ketones. In some embodiments, one of the two alkyl groups of the ketone is methyl. Mixtures of two or more aldehydes and / or ketones are also useful. Such hydrocarbon-substituted acylated agents and their preparation methods are disclosed in U.S. Patents: 5,840,920; 6,147,036; and 6,207,839.

[0064] In another embodiment, the hydrocarbon-substituted acylated agent may include a methylene bisphenol alkyl acid compound. Such compounds may be (i) aromatic compounds of the following formula:

[0065] R m -Ar-Z c (VI)

[0066] (ii) a condensation product of at least one carboxylic acid reactant such as compounds of formulas (IV) and (V) above, wherein in formula (VI): each R is independently a hydrocarbon group; m is 0 or an integer from 1 to 6, provided that m does not exceed the number of valences of the corresponding Ar group effectively used for substitution; Ar is an aromatic group or structural moiety comprising 5 to 30 carbon atoms and 0 to 3 optional substituents such as amino, hydroxy- or alkyl-polyoxyalkylene, nitro, aminoalkyl, and carboxyl, or a combination of two or more of the optional substituents; Z is independently -OH, -O, a lower alkoxy, or -(OR) 10 ) b OR 11 , where each R 10 Independently, it is a divalent hydrocarbon group, b is a number from 1 to 30, and R 11 It is -H or a hydrocarbon group; and c is a number from 1 to 3.

[0067] In one embodiment, at least one hydrocarbon group on the aromatic moiety is derived from polybutene. In another embodiment, the hydrocarbon group is derived from polybutene obtained by polymerizing isobutene in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. Such compounds and methods for their preparation are disclosed in U.S. Patents: 3,954,808; 5,336,278; 5,458,793; 5,620,949; 5,827,805; and 6,001,781.

[0068] In another embodiment, (i) and (ii) optionally, the reactions in the presence of an acidic catalyst such as an organic sulfonic acid, heteropoly acid, or inorganic acid can be carried out in the presence of at least one aldehyde or ketone. The aldehyde or ketone used in this embodiment is the same as those described above. Such compounds and methods for their preparation are disclosed in U.S. Patent 5,620,949. Other methods for preparing suitable hydrocarbon-substituted acylated agents can be found in U.S. Patents 5,912,213; 5,851,966; and 5,885,944.

[0069] The succinimide quaternary ammonium salt detergent is obtained by reacting the aforementioned hydrocarbon-substituted acylating agent with a compound having an oxygen or nitrogen atom capable of condensing with the acylating agent. In one embodiment, a suitable compound contains at least one tertiary amino group or can be alkylated until it contains a tertiary amino group, provided that the hydrocarbon-substituted acylating agent has at least one tertiary amino group upon quaternization.

[0070] In one embodiment, the compound may be represented by one of the following formulas:

[0071]

[0072] and

[0073]

[0074] In formulas (VII) and (VIII), each X is independently an alkylene group containing 1-4 carbon atoms; and each R is independently a hydrocarbon group, and R' is hydrogen or a hydrocarbon group.

[0075] Suitable compounds include, but are not limited to: 1-aminopiperidine, 1-(2-aminoethyl)piperidine, 1-(3-aminopropyl)-2-2-methylpiperidine, 1-methyl-(4-methylamino)piperidine, 1-amino-2,6-dimethylpiperidine, 4-(1-pyrrolyl)piperidine, 1-(2-aminoethyl)pyrrolidone, 2-(2-aminoethyl)-1-methylpyrrolidone, N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-dibutylethylenediamine, N,N,N'-trimethylethylenediamine, N,N-dimethyl- N'-Ethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N,N'-triethylethylenediamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, N,N,N'-trimethyl-1,3-propanediamine, N,N,2,2-tetramethyl-1,3-propanediamine, 2-amino-5-diethylaminopentane, N,N,N',N'-tetraethyldiethylenetriamine, 3,3'-diamino-N-methyldipropylamine, 3,3'-iminobis(N,N-dimethylpropylamine), or combinations thereof. In some embodiments, the amine used is 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 1-(2-aminoethyl)pyrrolidone, N,N-dimethylethylenediamine, N,N-diethylpropanediamine, or combinations thereof.

[0076] Suitable compounds further include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazolium and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3,3'-aminobis(N,N-dimethylpropylamine). These have been mentioned in the preceding enumerations.

[0077] Other nitrogen- or oxygen-containing compounds that can condense with acylating agents and also have a tertiary amino group include: alkanolamines, including but not limited to triethanolamine, triethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tri(hydroxyethyl)amine and N,N,N-tri(hydroxymethyl)amine.

[0078] The succinimide quaternary ammonium salt detergent of the present invention is formed by combining the above-described reaction product (a reaction product of a hydrocarbon-substituted acylating agent and a compound having an oxygen or nitrogen atom capable of condensing with said acylating agent and further having at least one tertiary amino group) with a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen. Suitable quaternizing agents are discussed in more detail below. In some embodiments, these preparations can be carried out purely or in the presence of solvents as described above. As a non-limiting example, the preparation of succinimide quaternary ammonium salts is provided below.

[0079] In some embodiments, the compositions of the present invention are substantially free of, or even completely free of, the aforementioned succinimide quaternary ammonium salt.

[0080] Polyalkylene-substituted amine quaternary ammonium salts

[0081] In one embodiment, the quaternary ammonium salt is a reaction product of the following components: (i)(b) a hydrocarbon-substituted amine having at least one tertiary amino group; and (ii) a quaternizing agent suitable for converting the tertiary amino group of compound (i) into a quaternary nitrogen group, wherein the hydrocarbon substituent is a polyalkylene substituent having a number average molecular weight of about 100 to about 500, or 100-450, or 150-400 or 200-350.

[0082] Suitable polyalkylene-substituted amines can be derived from olefin polymers and amines such as ammonia, monoamines, polyamines, or mixtures thereof. These can be prepared by a variety of methods. Suitable polyalkylene-substituted amines, or the amines from which they are obtained, contain a tertiary amino group or can be alkylated until they contain a tertiary amino group, provided that the polyalkylene-substituted amine has at least one tertiary amino group upon quaternization.

[0083] One method for preparing polyalkylene-substituted amines involves reacting a halogenated olefin polymer with an amine, as disclosed in U.S. Patents 3,275,554, 3,438,757, 3,454,555, 3,565,804, 3,755,433, and 3,822,289. Another method for preparing polyalkylene-substituted amines involves reacting a hydroformylated olefin with a polyamine and hydrogenating the reaction product, as disclosed in U.S. Patents 5,567,845 and 5,496,383. Yet another method for preparing polyalkylene-substituted amines involves converting polyalkylene to the corresponding epoxide using conventional epoxidizing agents, with or without a catalyst, and converting epoxides to polyalkylene-substituted amines by reacting with ammonia or an amine under reducing ammoniation conditions, as disclosed in U.S. Patent 5,350,429. Another method for preparing polyalkylene-substituted amines involves hydrogenating β-aminonitrile prepared by reacting an amine with a nitrile, as disclosed in U.S. Patent 5,492,641. Yet another method for preparing polyalkylene-substituted amines involves hydroformylating polybutene or polyisobutylene with a catalyst such as rhodium or cobalt in the presence of CO, H2, and NH3 under elevated pressure and temperature, as disclosed in U.S. Patents 4,832,702, 5,496,383, and 5,567,845. The methods for preparing polyalkylene-substituted amines described above are for illustrative purposes only and are not intended to be exhaustive. The scope of the polyalkylene-substituted amines of this invention is not limited to the methods for their preparation disclosed above.

[0084] Polyalkylene-substituted amines can be derived from olefin polymers. The olefin polymers suitable for preparing the polyalkylene-substituted amines of this invention are the same as those described above.

[0085] Polyalkylene-substituted amines can be derived from ammonia, monoamines, polyamines, or mixtures thereof, including mixtures of different monoamines, mixtures of different polyamines, and mixtures of monoamines and polyamines (including diamines). Suitable amines include aliphatic, aromatic, heterocyclic, and carbocyclic amines.

[0086] In one implementation, the amine is characterized by the following formula:

[0087] R 12 R 13 NH (IX)

[0088] Where R 12 and R 13 Each is independently a hydrogen-substituted hydrocarbon, an amino-substituted hydrocarbon, a hydroxyl-substituted hydrocarbon, an alkoxy-substituted hydrocarbon, or an acylimide group, provided that R 12 and R 13No more than one of the amines may be hydrogen. The amine may be characterized by the presence of at least one primary (H₂N⁻) or secondary (HN⁻) amino group. These amines, or polyalkylene-substituted amines prepared using them, may be alkylated as needed to ensure they contain at least one tertiary amino group. Examples of suitable monoamines include ethylamine, dimethylamine, diethylamine, n-butylamine, dibutylamine, allylamine, isobutylamine, cocoylamine, stearylamine, laurylamine, methyl laurylamine, oleylamine, N-methyl-octylamine, dodecylamine, diethanolamine, morpholine, and octadecylamine.

[0089] The polyamines that give detergents mainly include most alkylene amines that conform to the following formula:

[0090]

[0091] Where n is an integer usually less than 10, and each R 14 Alkylenes are either hydrogen or hydrocarbon groups having up to 30 carbon atoms, and are typically alkylenes having fewer than 8 carbon atoms. Alkylenes primarily include ethylenediamines, hexyleneamines, heptamethines, octyleneamines, and other polymethylamines. Specific examples include: ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, decamethyldiamine, octamethyldiamine, di(heptamethyl)triamine, tripropylenetetramine, tetraethylenepentamine, triethylenediamine, pentaethylenehexamine, di(-triethylene)triamine, aminopropylmorpholine, and dimethylaminopropylamine. Higher-order homologues, such as those obtained by condensing two or more of the above-mentioned alkylenes, are also useful. Tetraethylenepentamine is particularly useful.

[0092] Ethylenes, also known as polyethylene polyamines, are particularly useful. They are described in more detail in the title “Ethylene Amines”, Encyclopedia of Chemical Technology, Kirk and Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950).

[0093] The above polyalkylene-substituted amines, or any of the amines that yield them, can be alkylated into tertiary amines by an alkylating agent before or simultaneously with the reaction of the alkylating agent to form the quaternary ammonium salt additive of the present invention. Suitable alkylating agents include the quaternizing agents described below.

[0094] The polyalkylene-substituted amine quaternary ammonium salts of the present invention are formed by combining the above-described reaction product (a polyalkylene-substituted amine having at least one tertiary amino group) with a quaternizing agent suitable for converting the tertiary amino group into a quaternary nitrogen. Suitable quaternizing agents are described in more detail below. As a non-limiting example, the preparation of polyalkylene-substituted amine quaternary ammonium salts is provided below.

[0095] In some embodiments, the compositions of the present invention are substantially free of, or even completely free of, the aforementioned polyalkylene-substituted amine quaternary ammonium salts.

[0096] Polyether-substituted amine quaternary ammonium salts

[0097] In one embodiment, the quaternary ammonium salt is a reaction product of the following components: (i)(b) a hydrocarbon-substituted amine having at least one tertiary amino group; and (ii) a quaternizing agent suitable for converting the tertiary amino group of compound (i) into a quaternary nitrogen group, wherein the hydrocarbon substituent is a polyether substituent having a number average molecular weight of about 100 to about 500, or 100-450, or 150-400 or 200-350.

[0098] Suitable polyether-substituted amines can be derived from the reaction of polyethers and amines. They can be prepared by a variety of methods. Suitable polyether-substituted amines, or the amines from which they are obtained, contain a tertiary amino group or can be alkylated until they contain a tertiary amino group, provided that the polyether-substituted amine has at least one tertiary amino group upon quaternization.

[0099] The polyether of polyetheramine can be prepared by condensing an alcohol or alkylphenol of the following general formula with an oxidized alkene, a mixture of oxidized alkenes, or several oxidized alkenes in a sequential manner at a hydroxyl compound: oxidized alkene molar ratio of 1:1 to 50 to form a polyether:

[0100] R 3 OH

[0101] Where R 3 The groups are alkyl, alkenyl, optionally monounsaturated or polyunsaturated cycloalkyl, or aryl, each optionally substituted with at least one hydroxyl or alkyl group or separated by at least one heteroatom. U.S. Patent Nos. 5,112,364 and 5,264,006 provide reaction conditions for the preparation of polyethers. Alkyl means a saturated, linear, or branched hydrocarbon group having 1-4, 1-6, 1-8, 1-10, 1-14, or 1-20 carbon atoms; alkenyl means a monounsaturated, linear, or branched hydrocarbon group having 2-4, 2-6, 2-8, 2 to 10 or 20 carbon atoms and a double bond at any position; cycloalkyl means a carboxyl group having 3 to 20 carbon atoms; and aryl means a mononuclear, monocyclic, or bicyclic optionally substituted aromatic group having 6 to 10 or 20 cyclic carbon atoms.

[0102] Alcohols can be mono- or poly-ary, linear or branched, saturated or unsaturated, cyclic and aromatic, and have 1-40 carbon atoms, or 2-35 carbon atoms, or 4-30, or 8-20 carbon atoms. Branched alcohols can include Guerbert alcohols as described in U.S. Patent No. 5,264,006, which typically contain 12-40 carbon atoms and can be represented by the following formula:

[0103] R5 CH(CH2CH2R 5 CH2OH

[0104] Among them, each R 5 It is independently a hydrocarbon group. In one embodiment, the alkyl group of the alkylphenol may be 1-40 carbon atoms, or 2-24 carbon atoms, or 3-18 carbon atoms.

[0105] In one embodiment, the olefin oxide condensed with an alcohol to prepare the polyether may comprise a 1,2-epoxyalkane having 2-18 carbon atoms, or 2-6 carbon atoms. In yet another embodiment, the olefin oxide may be ethylene oxide, propylene oxide, or butene oxide. Propylene oxide, butene oxide, or mixtures thereof are particularly useful. The number of olefin oxide units in the polyether intermediate may be 1-10, 2-8, or 4-6.

[0106] The polyether used to prepare polyether-substituted amines can be represented by the following formula:

[0107] R 1 O[CH2CH(R 2 )O] q H

[0108] Where R 1 It is a hydrocarbon group, R 2 The group is selected from hydrogen, hydrocarbon groups having 1-16 carbon atoms, and mixtures thereof, where q is a number from 2 to 50. Polyethers may include compounds having two or more consecutive ether groups.

[0109] One method for preparing polyether-substituted amines involves reacting the aforementioned polyethers as intermediates and converting them into polyether amines. Polyether intermediates can be converted into polyether amines by several methods. Polyether intermediates can be converted into polyether amines by reductive amination with ammonia, a primary amine, or a polyamine, as described in U.S. Patent Nos. 5,112,364 and 5,752,991. In one embodiment, the polyether intermediate can be converted into a polyether amine by an addition reaction of the polyether with acrylonitrile to form a nitrile, followed by hydrogenation to form a polyether amine. U.S. Patent No. 5,264,006 provides reaction conditions for cyanoethylating a polyether with acrylonitrile, followed by hydrogenation to form a polyether amine. In yet another embodiment, the polyether intermediate or poly(oxyenol) alcohol is converted into the corresponding poly(oxyenol) chloride by a suitable chlorinating agent, whereby the chlorine is replaced with ammonia, a primary or secondary amine, or a polyamine, as described in U.S. Patent No. 4,247,301.

[0110] Polyether-substituted amines can have the following general formula:

[0111] (R 6 (R) 7 )NA-OH

[0112] Where R 6 and R 7 For the same or different, and representing alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl, or aminoalkenyl, or R 6 and R 7 A is a alkylene group, an aminoalkylene group, or an oxyalkylene group, wherein A is optionally a straight-chain or branched alkylene or alkenylene group separated by one or more heteroatoms such as N, O, and S.

[0113] Polyether-substituted amine quaternary ammonium salts can be formed by combining the above reaction product (a polyether-substituted amine having at least one tertiary amino group) with a quaternizing agent suitable for converting the tertiary amino group into a quaternary nitrogen. Suitable quaternizing agents are discussed in more detail below.

[0114] In some embodiments, the compositions of the present invention are substantially free of, or even completely free of, the aforementioned polyether-substituted amine quaternary ammonium salts.

[0115] Polyester quaternary ammonium salt

[0116] In some embodiments, the hydrocarbon substituent of the quaternary ammonium salt is a polyester having a number average molecular weight of about 100 to about 500, or 100-450, or 150-400 or 200-350. The polyester quaternary salt may include quaternized polyesteramines, amides, and ester salts. Such additives may also be described as quaternary polyester salts. The additives of the present invention may be described as the reaction product of the following components: a polyester containing a tertiary amine; and a quaternizing agent suitable for converting the tertiary amine to a quaternary nitrogen. The quaternizing agent may be any of the reagents described above.

[0117] The polyester containing tertiary amino groups used to prepare the additives of the present invention can also be described as a non-quaternized polyester containing tertiary amino groups.

[0118] In some embodiments, the polyester is a reaction product of an aliphatic carboxylic acid containing at least one hydroxyl group and a compound having an oxygen or nitrogen atom capable of condensing with the acid and further having a tertiary amine. Suitable aliphatic carboxylic acids for preparing the above-described polyester can be represented by the following formula:

[0119]

[0120] Where R 1 It is hydrogen or a hydrocarbon group containing 1-20 carbon atoms, and R 2 It is a hydrocarbon-like group containing 1-20 carbon atoms. In some embodiments, R 1 It contains 1-12, 2-10, 4-8, or even 6 carbon atoms, and R 2 It contains 2-16, 6-14, 8-12, or even 10 carbon atoms.

[0121] In some embodiments, the fatty carboxylic acid used to prepare the polyester is 12-hydroxystearic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid, 4-hydroxydecanoic acid, 10-hydroxyundecanoic acid, or a combination thereof.

[0122] In some embodiments, a compound having an oxygen or nitrogen atom capable of condensing with the acid and having a tertiary amine is represented by the following formula:

[0123]

[0124] Where R 3 A hydrocarbon group containing 1-10 carbon atoms; R 4 A hydrocarbon group containing 1-10 carbon atoms; R 5 It is a hydrocarbon-like group containing 1-20 carbon atoms; and X 1 For O or NR 6 , where R 6 It is hydrogen or a hydrocarbon group containing 1-10 carbon atoms. In some embodiments, R 3 Containing 1-6, 1-2, or even 1 carbon atom, R 4 Containing 1-6, 1-2, or even 1 carbon atom, R 5 It contains 2-12, 2-8, or even 3 carbon atoms, and R 6 It contains 1-8 or 1-4 carbon atoms. In some of these embodiments, formula (XII) becomes:

[0125]

[0126] The definitions provided above still apply.

[0127] Examples of nitrogen- or oxygen-containing compounds capable of condensing with acylating agents and also having a tertiary amine, or compounds that can be alkylated into such compounds, include any of the materials described in the foregoing sections.

[0128] Nitrogen- or oxygen-containing compounds may further include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazolium and 4-(3-aminopropyl)morpholine.

[0129] In one embodiment, the nitrogen- or oxygen-containing compound is triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamino)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, or a combination thereof.

[0130] In some embodiments, compounds having oxygen or nitrogen atoms capable of condensing with the acid and further having a tertiary amino group include N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-diethylpropanediamine, or combinations thereof.

[0131] The quaternized polyester salt can be a quaternized polyesteramide salt. In such embodiments, the polyester containing a tertiary amine used to prepare the quaternized polyester salt is a polyesteramide containing a tertiary amine. In some of these embodiments, an amine or amino alcohol is reacted with a monomer, and then the resulting material is polymerized with other monomers to obtain a polyesteramide, which can then be quaternized.

[0132] In some embodiments, the quaternized polyester salt comprises a cation represented by the following formula:

[0133]

[0134] Where R 1 It is hydrogen or a hydrocarbon group containing 1-3 carbon atoms, and R 2 It is a hydrocarbon group containing 1-4 carbon atoms; R 3 A hydrocarbon group containing 1-3 carbon atoms; R 4 A hydrocarbon group containing 1-3 carbon atoms; R 5 It is a hydrocarbon-like group containing 1 or 2 to 6 carbon atoms; R 6 It is hydrogen or a hydrocarbon group containing 1-3 carbon atoms; n is a number from 1 to approximately 7 or from 1 to approximately 5; R 7 It is hydrogen, a hydrocarbon group containing 1-3 carbon atoms, or a hydrocarbon group containing 1-3 carbon atoms; and X 2 This is a group derived from a quaternizing agent. In some embodiments, R... 6 It is hydrogen.

[0135] As mentioned above, in some implementation schemes, R 1 It contains 1-2, 2-3, or 1 carbon atom, and R 2 It contains 1-2, 2-3, or 1 carbon atom, R 3 Containing 1-2, 2-3, or even 1 carbon atom, R 4 Containing 1-2, 2-3, or even 1 carbon atom, R 5 It contains 1-2, 2-3, or even 1 carbon atom, and R 6 It contains 1-2, 2-3, or even 1 carbon atom. In any of these embodiments, n can be 2-7, or 3-6, and R 7It can contain 1-2, 2-3, or 1 carbon atom. R 7 It can be an acyl group.

[0136] In these implementations, the quaternized polyester salt is essentially C 1-22 Or C 8-20 Fatty acid capping. Examples of suitable acids include oleic acid, palmitic acid, stearic acid, erucic acid, lauric acid, 2-ethylhexanoic acid, 9,11-linoleic acid, 9,12-linoleic acid, 9,12,15-linolenic acid, rosin acid, or combinations thereof.

[0137] The number average molecular weight (Mn) of the fully quaternized polyester salt of the present invention can be from about 100 to about 750, or from about 200 to about 700, or from about 100 to about 500.

[0138] The polyester used in this invention can be obtained by heating one or more hydroxycarboxylic acids or a mixture of hydroxycarboxylic acids and carboxylic acids, optionally in the presence of an esterification catalyst. The hydroxycarboxylic acid may have the formula HO-X-COOH, where X is a divalent saturated or unsaturated aliphatic group containing at least 8 carbon atoms, and where a hydroxyl group is present between the hydroxyl and carboxylic acid groups, or a mixture of such hydroxycarboxylic acid and a carboxylic acid without a hydroxyl group, containing at least 4 carbon atoms. The reaction can be carried out at a temperature of 160-200°C until the desired molecular weight is obtained. The acid value of the product can be measured after the esterification process, wherein the desired polyester has an acid value of 1-200 mg KOH / g or 10-150 mg KOH / g in some embodiments. The 1-200 mg KOH / g acid value range corresponds to a number average molecular weight of 56100-280. Water formed during the esterification reaction can be removed from the reaction medium, and this can be conveniently done by passing a nitrogen stream through the reaction mixture, or by reacting in the presence of a solvent such as toluene or xylene and distilling off the water as it forms.

[0139] The resulting polyester can then be separated in a conventional manner; however, the resulting polyester solution can be used when the reaction is carried out in the presence of an organic solvent in which it does not harm the subsequent application.

[0140] In the hydroxycarboxylic acid, the group represented by X may contain 12-20 carbon atoms, optionally with 8-14 carbon atoms between the carboxylic acid and the hydroxyl group. In some embodiments, the hydroxyl group is a secondary hydroxyl group.

[0141] Specific examples of such hydroxycarboxylic acids include ricinoleic acid, a mixture of 9- and 10-hydroxystearic acid (obtained by sulfonation of oleic acid followed by hydrolysis), and 12-hydroxystearic acid, as well as commercially available hydrogenated castor oil fatty acids containing minor amounts of stearic acid and palmitic acid in addition to 12-hydroxystearic acid.

[0142] The carboxylic acid that can be used together with hydroxycarboxylic acids to obtain these polyesters is preferably a saturated or unsaturated aliphatic carboxylic acid, especially an alkyl or alkenyl carboxylic acid containing a chain of 8-20 carbon atoms. Examples of such acids include lauric acid, palmitic acid, stearic acid, and oleic acid.

[0143] In one embodiment, the polyester is derived from commercial 12-hydroxystearic acid with a number-average molecular weight of about 1600. Polyesters such as this are described in more detail in British Patent Specifications Nos. 1373660 and 1342746.

[0144] In some embodiments, the components used to prepare the above-mentioned additives are substantially free of, substantially free of, or even completely free of polyester-free hydrocarbon-substituted acylating agents and / or polyester-free hydrocarbon-substituted diacylating agents, such as polyisobutylene. In some embodiments, these excluded reagents are reaction products of components such as long-chain hydrocarbons, typically polyolefins, reacting with monounsaturated carboxylic acids such as (i) α,β-monounsaturated C4-C 10 Dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid; (ii) derivatives of (i) such as anhydrides of (i) or mono- or diesters derived from C1-C5 alcohols; (iii) α,β-monounsaturated C3-C 10 Monocarboxylic acids such as acrylic acid and methacrylic acid; or derivatives of (iv)(iii), such as (iii) with general formula (R) 9 (R) 10 C = C(R) 11 )(CH(R 7 (R) 8 )) represents any C1-C5 alcohol-derived ester of a compound containing an olefinic bond, where R 9 and R 10 Each is independently a hydrogen or hydrocarbon group; R 11 R 7 and R 8 Each is independently a hydrogen or hydrocarbon group, preferably at least one of which is a hydrocarbon group containing at least 20 carbon atoms. In one embodiment, the substituted acylate is a dicarboxylic acid acylate. In some of these embodiments, the substituted acylate is polyisobutylene succinic anhydride.

[0145] "Substantially free" means that the components of this invention are primarily composed of materials different from the aforementioned hydrocarbon-substituted acylation agents, such that these reagents are not significantly involved in the reaction, and that the compositions of this invention do not contain significant amounts of additives derived from these reagents. In some embodiments, the components or compositions of this invention may contain less than 10% by weight of these reagents or additives derived from them. In other embodiments, the maximum permissible amount may be 5, 3, 2, 1, or even 0.5 or 0.1% by weight. One objective of these embodiments is to allow the exclusion of reagents such as polyisobutylene succinic anhydride from the reactions of this invention, and therefore, also to allow the exclusion of quaternary ammonium salt detergent additives derived from reagents such as polyisobutylene succinic anhydride. The focus of this embodiment is polyester or hyperdispersant, quaternary salt detergent additives.

[0146] In some embodiments, the compositions of the present invention are substantially free of, or even completely free of, the aforementioned polyester quaternary salts.

[0147] Mannich Quaternary Ammonium Salt

[0148] In one embodiment, the quaternary ammonium salt is a reaction product of the following components: (i) (c) Mannich reaction products; and (ii) a quaternizing agent suitable for converting the tertiary amino group of compound (i) into a quaternary nitrogen. Suitable Mannich reaction products have at least one tertiary amino group and are prepared by reactions of phenols, aldehydes, and amines with hydrocarbon substitution.

[0149] The hydrocarbon substituent in a hydrocarbon-substituted phenol may have 1-36 carbon atoms, in another case 2-34 carbon atoms, and in yet another case 5 or 8 to 30 carbon atoms. This hydrocarbon substituent may be derived from an olefin or a polyolefin. Useful olefins include α-olefins, such as 1-decene, which are commercially available. Suitable polyolefins include those described in the preceding sections. Hydrocarbon-substituted phenols can be prepared by alkylating phenol with one of these suitable olefins or polyolefins, such as polyisobutylene or polypropylene, using well-known alkylation methods.

[0150] The aldehydes used to form Mannich detergents can have 1-10 carbon atoms and are usually formaldehyde or its reactive equivalents, such as formaldehyde water or paraformaldehyde.

[0151] The amine used to form the Mannich detergent can be a monoamine or a polyamine. The amines suitable for preparing the Mannich reaction products of this invention are the same as those described in the foregoing sections.

[0152] In one embodiment, the Mannich detergent is prepared by reacting a hydrocarbon-substituted phenol, aldehyde, and amine, as described in U.S. Patent 5,697,988. In one embodiment, the Mannich reaction product is prepared from the following components: an alkylphenol derived from polyisobutylene; formaldehyde; and a primary monoamine, secondary monoamine, or alkylene diamine. In some of these embodiments, the amine is ethylenediamine or dimethylamine. Other methods for preparing suitable Mannich reaction products can be found in U.S. Patents 5,876,468 and 5,876,468.

[0153] As mentioned above, it may be necessary to further react the Mannich reaction product with epoxides or carbonates or other alkylating agents using some amines to obtain tertiary amines.

[0154] The Mannich quaternary ammonium salts of the present invention are formed by combining the above-mentioned reaction product (a Mannich reaction product having at least one tertiary amino group) with a quaternizing agent suitable for converting the tertiary amino group into a quaternary nitrogen. Suitable quaternizing agents are discussed below.

[0155] In some embodiments, the compositions of the present invention are substantially free of, or even completely free of, the aforementioned Mannich quaternary ammonium salts.

[0156] Amides and / or ester quaternary ammonium salts

[0157] In some embodiments, the quaternary ammonium salt used in this invention is a quaternary amide and / or ester detergent that can be described as a reaction product of the following components: (i) a non-quaternized amide and / or ester detergent having tertiary amine functionality; and (ii) a quaternizing agent. In some embodiments, the non-quaternized detergent is a condensation product of (a) a hydrocarbon-substituted acylating agent and (b) a compound having an oxygen or nitrogen atom capable of condensing with said acylating agent and further having at least one tertiary amino group.

[0158] Non-quaternized amide and / or ester detergents suitable for use in this invention comprise (i) a hydrocarbon-substituted acylating agent and (ii) a condensation product of a compound having an oxygen or nitrogen atom capable of condensing with said acylating agent and further having at least one tertiary amino group, wherein the resulting detergent has at least one tertiary amino group and also comprises an amide group and / or an ester group. Generally, the presence of an oxygen or nitrogen atom capable of condensing with said acylating agent determines whether the resulting detergent contains an amide group or an ester group. In some embodiments, the non-quaternized detergent and all resulting quaternized detergents are free of any imide groups. In some embodiments, the non-quaternized detergent and all resulting quaternized detergents are free of any ester groups. In these embodiments, the detergent contains at least one, or exactly one, amide group.

[0159] The hydrocarbon-substituted acylated agent can be any material described in the above sections, provided that the material contains an amide group and / or an ester group.

[0160] When the above-described acylating agent reacts with a compound having an oxygen or nitrogen atom capable of condensing with the acylating agent and further having at least one tertiary amino group, a non-quaternary ammonium amide and / or ester detergent itself is formed for preparing the additives of the present invention. Any of these compounds may also be used herein.

[0161] In one embodiment, the non-quaternized amide and / or ester group may comprise a hydrocarbon-substituted dicarboxylic acid, such as succinic acid, without any imide group, wherein one carboxylic acid structural portion reacts with a compound having an oxygen or nitrogen atom capable of condensing with an acylating agent to form an amide, and other carboxylic acid structural portions retain acid groups. In another embodiment, the non-quaternized amide and / or ester group may comprise a hydrocarbon-substituted dicarboxylic acid, such as succinic acid, without any anhydride group, wherein one carboxylic acid structural portion reacts with a compound having an oxygen or nitrogen atom capable of condensing with an acylating agent to form an ester, and other carboxylic acid structural portions retain acid groups.

[0162] In other embodiments, non-quaternized amide and / or ester groups may be represented by the following formula:

[0163]

[0164] Where: R 21 A hydrocarbon group containing 1-3 carbon atoms; R 22 A hydrocarbon group containing 1-3 carbon atoms; R 23 It is a hydrocarbon group containing 1-3 carbon atoms; R 24 It is a hydrocarbon group containing 7-36 carbon atoms; and Y is NH or O.

[0165] Quaternary amides and / or ester detergents are prepared by reacting (a) a non-quaternized amide and / or ester detergent with tertiary amine functionality with (b) a quaternizing agent; thereby obtaining a quaternized detergent. The method of the present invention can also be described as a method for preparing quaternized amides and / or ester detergents, comprising the steps of: (1) mixing (a) a non-quaternized amide and / or ester detergent with amine functionality, (b) a quaternizing agent, and optionally (c) a protic solvent free of methanol in some embodiments; (2) heating the mixture to a temperature of 50-130°C; and (3) maintaining the reaction until complete; thereby obtaining a quaternized amide and / or ester detergent. In one embodiment, the reaction is carried out at a temperature less than 80°C or less than 70°C. In other embodiments, the reaction mixture is heated to a temperature of about 50°C to 120°C, 80°C, or 70°C. In yet another embodiment in which the alkyl acylating agent is derived from a monocarboxylic acid, the reaction temperature may be 70-130°C. In other embodiments where the alkyl acylating agent is derived from a dicarboxylic acid, the reaction temperature can be 50-80°C or 50-70°C. In some embodiments, the method of the present invention does not involve the addition of any acid reactants such as acetic acid. In these embodiments, a salt product is obtained, although no separate acid reactants are present.

[0166] As described above, in some embodiments, the non-quaternized amide and / or ester detergent is a condensation product of a hydrocarbon-substituted acylating agent and a compound having an oxygen or nitrogen atom capable of condensing with said acylating agent and further having at least one tertiary amino group. Suitable quaternizing agents and compounds having oxygen or nitrogen atoms are also described above.

[0167] The additives of this invention can be obtained in the presence of a proton solvent. In some embodiments, the methods for preparing these additives are substantially free of methanol to be methanol-free. "Substantially free" may mean less than 0.5, 0.1, or 0.05% by weight of methanol in the reaction mixture, and may mean completely free of methanol.

[0168] Suitable proton solvents include solvents having a dielectric constant greater than 9. In one embodiment, the proton solvent includes compounds containing one or more hydroxyl functional groups and may include water.

[0169] In one embodiment, the solvent is a glycol and a glycol ether. Glycols containing 2-12 carbon atoms, or 4-10, or 6-8 carbon atoms, and their oligomers (e.g., dimers, trimers, and tetramers) are generally suitable. Illustrative glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, triethylene glycol, polyethylene glycol, and the like, as well as oligomers and polymeric derivatives and mixtures thereof. Illustrative glycol ethers include C1-C6 alkyl ethers of propylene glycol, ethylene glycol, and their oligomers, such as di-, tri-, and tetraethylene glycol ethers of methyl, ethyl, propyl, butyl, or hexyl. Suitable glycol ethers include ethers of dipropylene glycol, tripropylene glycol, diethylene glycol, and triethylene glycol; ethyl diethylene glycol ethers, butyl diethylene glycol ethers, methoxy triethylene glycol, ethoxy triethylene glycol, butoxy triethylene glycol, methoxy tetraethylene glycol, and butoxy tetraethylene glycol.

[0170] Solvents suitable for use in this invention also include certain alcohols. In one embodiment, these alcohols contain at least 2 carbon atoms; in other embodiments, at least 4, at least 6, or at least 8 carbon atoms. In another embodiment, the solvents of this invention contain 2-20 carbon atoms, 4-16 carbon atoms, 6-12 carbon atoms, 8-10 carbon atoms, or exactly 8 carbon atoms. These alcohols typically have a 2-(C) group. 1-4 Alkyl substituents, i.e., any isomer of methyl, ethyl, propyl, or butyl. Examples of suitable alcohols include 2-methylheptanol, 2-methyldecanol, 2-ethylpentanol, 2-ethylhexanol, 2-ethylnonanol, 2-propylheptanol, 2-butylheptanol, 2-butyloctanol, isooctanol, dodecyl alcohol, cyclohexanol, methanol, ethanol, propan-1-ol, 2-methylpropan-2-ol, 2-methylpropan-1-ol, butan-1-ol, butan-2-ol, pentanol, and their isomers, and mixtures thereof. In one embodiment, the solvent of the present invention is 2-ethylhexanol, 2-ethylnonanol, 2-propylheptanol, or a combination thereof. In one embodiment, the solvent of the present invention comprises 2-ethylhexanol.

[0171] The solvent can be any commercially available alcohol or a mixture of such alcohols, including mixtures of such alcohols and alcohols with water. In some embodiments, the amount of water present can be more than 1% by weight of the solvent mixture. In other embodiments, the solvent mixture may contain trace amounts of water, wherein the water content is less than 1% or 0.5% by weight.

[0172] Alcohols can be aliphatic, alicyclic, aromatic, or heterocyclic, including aliphatic-substituted alicyclic alcohols, aliphatic-substituted aromatic alcohols, aliphatic-substituted heterocyclic alcohols, alicyclic-substituted aliphatic alcohols, alicyclic-substituted aromatic alcohols, alicyclic-substituted heterocyclic alcohols, heterocyclic-substituted aliphatic alcohols, heterocyclic-substituted alicyclic alcohols, and heterocyclic-substituted aromatic alcohols.

[0173] Despite a reluctance to be bound by theory, it is believed that polar protic solvents are required to promote the dissociation of acids into ions and protons. Dissociation is required to protonate the ions formed when a detergent with amine functionality first reacts with a quaternizing agent. In the case of an alkyl epoxide as the quaternizing agent, the resulting ions are unstable alkoxide ions. Dissociation also provides counterions from the acid groups of the additive, which stabilize the quaternary ammonium ions formed in the reaction, resulting in a more stable product.

[0174] A solvent may be present such that the weight ratio of the amount of the amine-functionalized detergent to the amount of the polar solvent is 20:1 to 1:20; or 10:1 to 1:10 in one set of embodiments. In another embodiment, the detergent:solvent weight ratio is 1:10 to 1:15; 15:1 to 10:1; or 5:1 to 1:1.

[0175] In some embodiments, the compositions of the present invention are substantially free of, or even completely free of, the aforementioned quaternamides and / or ester detergents.

[0176] Quaternizing agent

[0177] Suitable quaternizing agents for preparing any of the above-mentioned quaternary ammonium salt detergents include dialkyl sulfates, benzyl halides, hydrocarbon-substituted carbonates, hydrocarbon epoxides used in combination with acids, esters of polycarboxylic acids, or mixtures thereof.

[0178] In one embodiment, the quaternizing agent includes: a halide, such as a chloride, iodide, or bromide; a hydroxide; a sulfonate; an alkyl sulfate ester, such as dimethyl sulfate; a sulfonyl lactone; a phosphate; or C. 1-12 Alkyl phosphate; di-C 1-12 Alkyl phosphates; borates; C 1-12 Alkyl borate; nitrite; nitrate; carbonate; bicarbonate; alkoxide; O,O-di-C 1-12 Alkyl dithiophosphate; or mixtures thereof.

[0179] In one embodiment, the quaternizing agent may be: a dialkyl sulfate ester, such as dimethyl sulfate; an N-oxide; a sulfonyl lactone, such as propane or butane sulfonyl lactone; an alkyl, acyl, or aralkyl halide, such as methyl and ethyl chlorides, bromides, or iodides, or benzyl chloride; a hydrocarbon (or alkyl) substituted carbonate; or a combination thereof. If the aralkyl halide is benzyl chloride, the aromatic ring may optionally be further substituted with an alkyl or alkenyl group.

[0180] The hydrocarbon (or alkyl) group in a hydrocarbon-substituted carbonate may contain 1-50, 1-20, 1-10, or 1-5, or 1-3 carbon atoms per group. In one embodiment, the hydrocarbon-substituted carbonate comprises two hydrocarbon groups that may be the same or different. Suitable hydrocarbon-substituted carbonates include dimethyl carbonate or diethyl carbonate.

[0181] In another embodiment, the quaternizing agent can be a hydrocarbon-based epoxide as shown in the following formula:

[0182]

[0183] Where R 15 R 16 R 17 and R 18 It can be H or C independently. 1-50 Hydrocarbon groups. Examples of suitable hydrocarbon-based epoxides include: styrene oxide, ethylene oxide, propylene oxide, butene oxide, mesopyrethylene oxide, and C... 2-50 Epoxides or combinations thereof.

[0184] In another embodiment, the quaternizing agent can be an ester of a carboxylic acid capable of reacting with a tertiary amine to form a quaternary ammonium salt, or an ester of a polycarboxylic acid. Generally, such materials can be described as compounds having the following structures:

[0185] R 19 -C(=O)-OR 20 (XV)

[0186] Where R 19 The substituted alkyl, alkenyl, aryl, or alkylaryl groups are optionally substituted, and R 20 It is a hydrocarbon group containing 1-22 carbon atoms.

[0187] Suitable compounds include esters of carboxylic acids having a pKa of 3.5 or less. In some embodiments, the compound is an ester of a carboxylic acid selected from substituted aromatic carboxylic acids, α-hydroxycarboxylic acids, and polycarboxylic acids. In some embodiments, the compound is an ester of a substituted aromatic carboxylic acid, therefore, R 19 The aryl group is substituted. R can be a substituted aryl, phenyl, or naphthyl group having 6-10 carbon atoms. R can be suitably substituted by one or more groups selected from: carbamoyloxy, nitro, cyano, hydroxyl, SR' or NR'R'', wherein R' and R'' can each be independently hydrogen, or optionally substituted alkyl, alkenyl, aryl, or carbamoyloxy. In some embodiments, R' and R'' are each independently hydrogen or optionally substituted alkyl groups containing 1-22, 1-16, 1-10, or even 1-4 carbon atoms.

[0188] In some implementations, R in the above formula 19 An aryl group substituted with one or more groups selected from the following: hydroxyl, carbamoyl, nitro, cyano, and NH. 2 R 19 It can be a polysubstituted aryl group, such as trihydroxyphenyl, but it can also be a monosubstituted aryl group, such as an ortho-substituted aryl group. R 19It can be substituted with groups selected from OH, NH2, NO2, or COOMe. Suitable, R 19 It is an aryl group substituted with a hydroxyl group. In some embodiments, R 19 It is a 2-hydroxyphenyl. R 20 It can be alkyl or alkylaryl, for example, alkyl or alkylaryl containing 1-16 carbon atoms, or 1-10, or 1-8 carbon atoms. R 20 It can be methyl, ethyl, propyl, butyl, pentyl, benzyl, or an isomer thereof. In some embodiments, R 20 It can be benzyl or methyl. In some embodiments, the quaternizing agent is methyl salicylate.

[0189] In some embodiments, the quaternizing agent is an ester of an α-hydroxycarboxylic acid. Such compounds applicable herein are described in EP 1254889. Examples of suitable compounds containing residues of α-hydroxycarboxylic acids include (i) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of 2-hydroxyisobutyric acid; (ii) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of 2-hydroxy-2-methylbutyric acid; (iii) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of 2-hydroxy-2-ethylbutyric acid; (iv) methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of lactic acid; and (v) methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, benzyl, and phenyl esters of glycolic acid. In some implementations, the quaternizing agent comprises methyl 2-hydroxyisobutyrate.

[0190] In some embodiments, the quaternizing agent comprises an ester of a polycarboxylic acid. In this definition, we mean dicarboxylic acids and carboxylic acids having more than two acidic structural moieties. In some embodiments, the ester is an alkyl ester having an alkyl group comprising 1-4 carbon atoms. Suitable examples include diesters of oxalic acid, phthalic acid, maleic acid, malonic acid, or citric acid.

[0191] In some embodiments, the quaternizing agent is an ester of a carboxylic acid having a pKa of less than 3.5. In such compounds, where the compound contains more than one acid group, we mean the first dissociation constant. The quaternizing agent may be selected from esters of carboxylic acids, wherein the carboxylic acid is selected from one or more of the following: oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzic acid, aminobenzoic acid, and 2,4,6-trihydroxybenzoic acid. In some embodiments, the quaternizing agent includes dimethyl oxalate, methyl 2-nitrobenzate, and methyl salicylate.

[0192] Any of the aforementioned quaternizations, including hydrocarbon epoxides, can be used in combination with an acid. Suitable acids include carboxylic acids, such as acetic acid, propionic acid, 2-ethylhexanoic acid, etc. In some embodiments, such as when the hydrocarbon acylating agent is a dicarboxylic acid acylating agent, a separate acid component is not required. In such embodiments, the detergent can be prepared by combining reactants that contain essentially no to no acid components such as acetic acid, but depend on the acid group of the hydrocarbon acylating agent.

[0193] In some embodiments, the quaternary ammonium salt comprises a reaction product of the following components: (i) a compound containing at least one tertiary amino group; and (ii) a quaternizing agent adapted to convert the tertiary amino group of compound (i) into a quaternary nitrogen, wherein component (i), the compound containing at least one tertiary amino group, comprises (a) a condensation product of a hydrocarbon-substituted acylating agent and a compound having an oxygen or nitrogen atom capable of condensing with the acylating agent, wherein the condensation product has at least one tertiary amino group.

[0194] In some embodiments, the hydrocarbon-substituted acylating agent may be polyisobutylene succinic anhydride, and the compound having oxygen or nitrogen atoms capable of condensing with said acylating agent may be dimethylaminopropylamine, dimethylethanolamine, diethylethanolamine, N-methyl-1,3-diaminopropane, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylaminoethylamine, diethylenetriamine, dipropylenetriamine, dibutyltriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine, and bis(hexamethylene)triamine.

[0195] In some embodiments, the quaternary ammonium salt comprises a cation represented by the following formula:

[0196]

[0197] Where: R 21 A hydrocarbon group containing 1-3 carbon atoms; R 22 A hydrocarbon group containing 1-3 carbon atoms; R 23 It is a hydrocarbon group containing 1-3 carbon atoms; R 24 It is a hydrocarbon group containing 7-36 carbon atoms; and X is a group derived from a quaternizing agent.

[0198] In some embodiments, the quaternary ammonium salt comprises a reaction product of the following components: (i) a compound containing at least one tertiary amino group; and (ii) a quaternizing agent adapted to convert the tertiary amino group of compound (i) into a quaternary nitrogen, wherein component (i), the compound containing at least one tertiary amino group, comprises: (b) a polyalkylene-substituted amine having at least one tertiary amino group.

[0199] In some embodiments, the polyalkylene substituents of the polyalkylene substituted amine are derived from polyisobutylene, and the polyalkylene substituted amine has a number average molecular weight of about 100 to about 500.

[0200] In some embodiments, the quaternary ammonium salt comprises a reaction product of the following components: (i) a compound containing at least one tertiary amino group; and (ii) a quaternizing agent adapted to convert the tertiary amino group of compound (i) into a quaternary nitrogen, wherein component (i), the compound containing at least one tertiary amino group, comprises: (c) a Mannich reaction product having at least one tertiary amino group, wherein the Mannich reaction product is derived from hydrocarbon-substituted phenols, aldehydes, and amines.

[0201] In some embodiments, component (i), a compound containing at least one tertiary amino group, comprises a Mannich reaction product having a tertiary amino group, said Mannich reaction product being prepared by reacting a hydrocarbon-substituted phenol, an aldehyde, and an amine; and wherein the hydrocarbon substituent of the hydrocarbon-substituted phenol of component (i) is derived from a polyolefin having a number average molecular weight of about 100 to 400; wherein the aldehyde of component (i) is formaldehyde or a reactive equivalent thereof; and wherein the amine of component (i) is selected from dimethylamine, ethylenediamine, dimethylaminopropylamine, diethylenetriamine, dibutylamine, and mixtures thereof.

[0202] In any of the above-described embodiments, any one or a combination of the above-described quaternizing agents may be used.

[0203] Industrial applications

[0204] In one embodiment, the invention is used as a liquid fuel for an internal combustion engine. The internal combustion engine includes spark-ignition and compression-ignition engines; two-stroke or four-stroke cycles; liquid fuel supplied by direct injection, indirect injection, or bore injection or a carburetor; common rail and unit injection systems; light-duty (e.g., passenger car) and heavy-duty (commercial truck) engines; and engines that burn hydrocarbon and exhaust hydrocarbon fuels and mixtures thereof. The engine may be part of a combined emissions system incorporating such elements; an EGR system; an aftertreatment system including a three-way catalyst, an oxidation catalyst, a NOx absorbent and catalyst, optionally using a fuel-based catalyst, and catalytic and non-catalytic particulate filters; variable valve timing; and injection timing and rate shaping.

[0205] In one embodiment, the composition may contain more than 3% by weight of a quaternary ammonium salt. In other embodiments, the composition may contain more than 4% by weight, or 5% by weight, or even 10% or 25% by weight of a quaternary ammonium salt.

[0206] In another embodiment, the composition may further comprise a higher molecular weight quaternary ammonium salt. The higher molecular weight quaternary ammonium salt may comprise (a) a compound comprising (i) at least one tertiary amino group as described above and (ii) a hydrocarbon substituent having a number average molecular weight of about 500 to about 5000, or up to 2500, or up to 1500; and (b) a quaternizing agent as described above suitable for converting the tertiary amino group of (a)(i) into a quaternary nitrogen. Higher molecular weight quaternary ammonium salts are more thoroughly described in U.S. Patent Nos. 7,951,211, filed May 31, 2011, and 8,083,814, filed December 27, 2011, and U.S. Publication Nos. 2008 / 0113890, published May 15, 2008, and 2011 / 0219674, published September 2011.

[0207] In some embodiments, compositions containing quaternary ammonium salts can be used in diesel fuels. In specific embodiments, the diesel fuel can be an ultra-low sulfur diesel fuel, meaning a diesel fuel having less than 30 ppm, or less than 20 ppm, or even less than 15 ppm of sulfur.

[0208] In one embodiment, the diesel fuel may contain about 10 to about 500 ppm of a quaternary ammonium salt composition. In another embodiment, the quaternary ammonium salt composition may be present in the diesel fuel at about 20 to about 250 ppm, or about 30 to about 120 ppm.

[0209] Quaternary ammonium salt compositions can be used in methods to minimize the formation of internal diesel injector deposits. Quaternary ammonium salts can also be used to reduce the level of pre-existing internal diesel injector deposits. In one embodiment, a quaternary ammonium salt composition can be used in a method to minimize the formation of internal diesel injector deposits while also reducing the level of pre-existing internal diesel injector deposits. Any of the foregoing methods includes the step of supplying a diesel fuel composition to a diesel engine comprising (A) diesel fuel; and (B) a quaternary ammonium salt composition as described herein. In one embodiment, the method may include adding the diesel fuel and composition to a diesel engine comprising a high-pressure common rail diesel injector.

[0210] As used herein, the term "hydrocarbon substituent" or "hydrocarbon group" is used in its common meaning as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the rest of the molecule and having predominantly hydrocarbon properties. Examples of hydrocarbon groups include: hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic substituted aromatic substituents, as well as cyclic substituents in which the ring is completed through another part of the molecule (e.g., two substituents forming a ring together); substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups (e.g., halogens (especially chlorine and fluorine), hydroxyl, alkoxy, mercapto, alkyl mercapto, nitro, nitroso, and sulfoxy) that do not alter the predominantly hydrocarbon properties of the substituent in the context of this invention; and heterosubstituents, i.e., substituents that, in the context of this invention, have predominantly hydrocarbon properties while containing substituents different from carbon in a ring or chain composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and substituents such as pyridyl, furanyl, thiophene, and imidazolyl. Generally, for every 10 carbon atoms, there are no more than 2, preferably no more than 1, non-hydrocarbon substituents in the hydrocarbon group; typically, there are no non-hydrocarbon substituents in the hydrocarbon group.

[0211] It is known that some of the above-mentioned materials may interact in the final formulation, such that the components of the final formulation may differ from those initially added. For example, metal ions (e.g., those of detergents) may migrate to other acidic or anionic sites of other molecules. The resulting products, including those formed by using the compositions of the present invention for their intended use, may not be easily described. However, all such modifications and reaction products are included within the scope of the present invention; the present invention includes compositions prepared by mixing the above-mentioned components.

[0212] Example

[0213] The following embodiments further illustrate the invention, describing particularly advantageous implementations. Although embodiments are provided to illustrate the invention, they are not intended to limit it.

[0214] Comparative sample A:

[0215] Comparative sample A was prepared from a mixture of succinic anhydrides, which was derived from 350 g of 210 Mn polyisobutylene and heated to 105 °C with stirring under a nitrogen atmosphere. Tetraethylpentamine (TEPA, 293.9 g) was slowly added over approximately 1 hour, while maintaining the batch temperature below 120 °C. The reaction temperature was then increased to 175 °C and maintained for another 4.5 hours. The resulting compound was TEPA succinimide.

[0216] Preparation of sample 1

[0217] Sample 1 was prepared from a mixture of succinic anhydrides, which was prepared from 210Mn polyisobutylene (800 g) and heated to 105 °C with stirring under a nitrogen atmosphere. Dimethylaminopropylamine (DMAPA, 289.9 g) was slowly added over 95 minutes, maintaining the batch temperature below 120 °C. The reaction temperature was then increased to 150 °C and maintained for another 3 hours. The resulting compound was DMAPA succinimide. 1109 g of the obtained DMAPA succinimide was then heated to reflux (~80 °C) with propylene oxide (257.8 g), acetic acid (177.75 g), and 2-ethylhexanol (1156.5 g) under a nitrogen atmosphere with stirring. The resulting compound was a propylene oxide quaternary ammonium salt.

[0218] Preparation of sample 2

[0219] Sample 2 was prepared from a mixture of 12-hydroxystearic acid (550.2 g) and heated to 100 °C with stirring under a nitrogen atmosphere. Dimethylaminopropylamine (DMAPA, 205.5 g) was slowly added over 23 minutes and maintained at 100 °C for 3.5 hours, then heated to 110 °C and maintained for 17 hours, followed by a final heating to 120 °C and maintained for 6.5 hours. The resulting compound was a fatty amide. The obtained fatty amide (534.6 g), propylene oxide (149.57 g), acetic acid (77.6 g), and water (5.35 g) were heated to reflux (~80 °C) with stirring under a nitrogen atmosphere. The resulting compound was a propylene oxide quaternary ammonium salt.

[0220] Examples 1-5—Scale Deposits Test

[0221] Detergents were evaluated in a direct injection fouling test. The test was described as follows: Ultra-low sulfur fuel (<15ppm S) with various detergents* was injected into a John Deere 6068 Tier III Powertech 6.8L 250hp engine. The torque at the start of the test was consistently 804-850 Nm. The engine was run at 95% load or 95% power capacity, with the engine maneuverable and maintained at 1400 rpm before shutdown. The engine was kept at 95% load (as measured by computer) for 8 hours of operation, then shut down and allowed to soak for 4 hours. During operation, if the % load reached the 98-99% range, the torque was adjusted downwards until the % load returned to 95%. When the load reached the 92-93% range, the reverse method was used. For each cylinder, torque measurements were taken every 6 minutes along with exhaust gas temperature. After the test, the injectors were removed and cleanliness was evaluated. In evaluating the effectiveness of the additives, all three of the following factors were considered: power loss, exhaust gas temperature change, and injector viscosity. Minimal power loss, temperature variation, and injector viscosity are required. The test results are summarized in Table 1.

[0222] *Note: In Examples 1, 2 and 4, the active chemical is specified as TOFA, which is accompanied by tall oil fatty acids (TOFA).

[0223] Table 1: Results of the fouling test

[0224]

[0225] The test results showed that control sample A performed poorly in the fouling test, and TOFA acted as a neutral dispersant. In contrast, the formulation using the quaternary ammonium salt detergent of this invention did not foul.

[0226] Example 6—Cleaning Experiment

[0227] If Sample 1 does not show fouling, its cleanliness is tested in a direct injection cleaning test. The test is described below. A mixture of ultra-low sulfur diesel fuel and fouling agent is filled into a John Deere 6068 Tier III Powertech 6.8L 250hp engine. The engine is run at 1400 rpm and 95% load. The engine is maintained under these operating conditions for an 8-hour run-time test, then shut down and allowed to soak for 4 hours. During operation, if the % load reaches the 98-99% range, the torque is adjusted downwards until the % load returns to 95%. When the load reaches the 92-93% range, the opposite method is used. After a 32-hour run-time test, the additive preparation Sample 1 is mixed with the fuel mixture to be injected into the engine. Other cycles are performed until a 49-hour run-time test is completed. For each cylinder, torque measurements are taken every 6 minutes along with exhaust gas temperature. The changes in exhaust gas temperature from 0 to 32 hours, 32 to 49 hours, and throughout the entire test are summarized in Table 2, and the changes in torque from 0 to 32 hours, 32 to 49 hours, and throughout the entire test are summarized in Table 3.

[0228] Table 2: Exhaust gas temperature results in the cleanliness test

[0229]

[0230]

[0231] Table 3: Torque and Injector Results in Cleaning Test

[0232]

[0233] Test results show that the quaternary ammonium salt detergent of this invention can effectively clean fuel injectors.

[0234] The foregoing documents are incorporated herein by reference. Unless otherwise expressly stated in the examples or elsewhere, all quantities of materials, reaction conditions, molecular weights, carbon numbers, etc., described in this specification should be understood to be modified by the word “about.” Unless otherwise stated, all quantities of materials or ratios described are based on weight. Unless otherwise stated, each chemical or composition mentioned herein should be understood as a commercial-grade material that may contain isomers, byproducts, derivatives, and other such materials that should generally be understood to be present in commercial-grade materials. However, unless otherwise stated, the quantities of each chemical component are expressed excluding any solvents or diluents that are generally present in commercial materials. It should be understood that the upper and lower limits of the quantities, ranges, and ratios described herein can be combined independently. Similarly, the ranges and quantities of each element of the invention can be used in conjunction with the ranges or quantities of any other element. As used herein, the expression “consisting essentially of…” allows for the inclusion of substances that do not substantially affect the essential and novel characteristics of the composition under consideration.

Claims

1. A method of minimizing the production of internal diesel injector deposits while also reducing the level of pre-existing internal diesel injector deposits comprising the step of supplying to a diesel engine a diesel fuel composition comprising (A) a diesel fuel; and (B) a composition comprising a quaternary ammonium salt, wherein the quaternary ammonium salt comprises the reaction product of: a) a compound comprising: (i) at least one tertiary amino group, and (ii) a hydrocarbyl substituent derived from a hydrocarbon having a number average molecular weight of from 100 to 450; b) a quaternization agent suitable for converting the tertiary amino group of compound (a) to a quaternary nitrogen, said quaternization agent comprising propylene oxide used in combination with an acid; and wherein the quaternary ammonium salt has a cation represented by the formula: ###0001### wherein: R1 is a hydrocarbyl group having from 1 to 20 carbon atoms; R2 is a hydrocarbyl group having from 1 to 20 carbon atoms; R3 is a hydrocarbyl group having from 1 to 20 carbon atoms; and R4 is a hydrocarbyl group having from 1 to 20 carbon atoms.

2. The method according to claim 1 wherein component a), the compound comprising at least one tertiary amino group, comprises the condensation product of a hydrocarbyl- substituted acylating agent and a compound having a nitrogen atom capable of condensing with said acylating agent and further having at least one tertiary amino group; and wherein the hydrocarbyl-substituted acylating agent is polyisobutylene succinic anhydride and the compound having a nitrogen atom capable of condensing with said acylating agent is N,N-dimethyl-aminopropylamine.

3. The method according to claim 1 wherein the diesel fuel is an ultra low sulfur diesel fuel comprising less than 30 ppm sulfur.

4. The method according to claim 2 wherein the diesel fuel is an ultra low sulfur diesel fuel comprising less than 30 ppm sulfur.

5. The method according to any one of claims 1 to 4 wherein the quaternary ammonium salt is present at from 10 to 500 ppm.

6. The method according to any one of claims 1 to 4 wherein the diesel engine comprises a high pressure common rail diesel injector.

7. The method according to claim 5 wherein the diesel engine comprises a high pressure common rail diesel injector. R 21 is a hydrocarbyl group containing 1 to 3 carbon atoms; R 22 is a hydrocarbyl group containing 1 to 3 carbon atoms; R 23 is a hydrocarbylene group containing 1 to 3 carbon atoms; R 24 is a hydrocarbyl group having 7 to 36 carbon atoms; and X is a group derived from a quaternizing agent.

8. A diesel fuel comprising a composition as defined in any one of the preceding claims.

9. The diesel fuel according to claim 8 wherein the diesel fuel is an ultra low sulfur diesel fuel comprising less than 30 ppm sulfur.

10. The diesel fuel according to claim 8 or 9 wherein the quaternary ammonium salt is present at from 10 to 500 ppm.

11. Use of a diesel fuel as defined in any one of claims 8 to 10 to reduce and control deposit formation, reduce fuel consumption, promote drivability, or reduce emissions in an engine supplied with said fuel.

12. A method of reducing and controlling deposit formation, reducing fuel consumption, promoting drivability, or reducing emissions in an engine, said method comprising supplying to said engine a diesel fuel as defined in any one of claims 8 to 10. ​ ​ ​ ​ ​ ​ ​

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