QUATERNIZED NITROGEN COMPOUNDS WITH ALKYLENE OXIDE AND HYDROCARBYL-SUBSTITUTED POLYCARBOXYLIC ACID AS ADDITIVES IN FUELS

Description

[0001] The present invention relates to fuel compositions containing quaternized nitrogen compounds in a special manner. These additives act in particular as detergent additives; for reducing or preventing deposits in the injection systems of direct-injection diesel engines, especially in common-rail injection systems; for reducing fuel consumption in direct-injection diesel engines, especially in diesel engines with common-rail injection systems; and for minimizing power loss in direct-injection diesel engines, especially in diesel engines with common-rail injection systems; and as an additive for gasoline fuels, especially for operating DISI engines. State of the art:

[0002] In direct-injection diesel engines, the fuel is injected through a multi-hole injection nozzle extending directly into the engine's combustion chamber and dispersed (atomized) as finely as possible, rather than being introduced into a pre-chamber or swirl chamber as in a conventional (chamber) diesel engine. The advantage of direct-injection diesel engines is their high performance for a diesel engine while maintaining low fuel consumption. These engines also achieve very high torque even at low engine speeds.

[0003] There are currently three main methods used to inject fuel directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the pump-nozzle system (unit injector system or unit pump system) and the common rail system.

[0004] In the common rail system, diesel fuel is pumped into a high-pressure line, the common rail, by a pump at pressures of up to 2000 bar. Branch lines from the common rail lead to the various injectors, which inject the fuel directly into the combustion chamber. The common rail is always at full pressure, enabling multiple injection or a special injection pattern.

[0005] With other injection systems, however, only a smaller variation in injection is possible. Common rail injection is essentially divided into three groups: (1) pre-injection, which essentially achieves softer combustion, thus reducing harsh combustion noises ("knocking") and making the engine run smoothly; (2) main injection, which is particularly responsible for a good torque curve; and (3) post-injection, which particularly ensures a low NOx level. During this post-injection, the fuel is generally not burned but evaporated by residual heat in the cylinder. The resulting exhaust / fuel mixture is transported to the exhaust system, where the fuel, in the presence of suitable catalysts, acts as a reducing agent for the nitrogen oxides (NOx).

[0006] Through variable, cylinder-specific injection, the common-rail injection system can positively influence the engine's pollutant emissions, such as nitrogen oxides (NO x ), carbon monoxide (CO), and especially particulates (soot). This allows, for example, engines equipped with common-rail injection systems to theoretically meet the Euro 4 standard without an additional particulate filter.

[0007] In modern common-rail diesel engines, under certain conditions, for example, when using fuels containing biodiesel or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds, and other metal compounds, deposits can form at the injector openings. These deposits negatively impact the fuel injection behavior and thus impair engine performance, particularly reducing power, but also sometimes worsening combustion. The formation of deposits is further exacerbated by further developments in the design of the injectors, particularly by changes to the geometry of the nozzles (narrower, conical openings with a rounded outlet). For the long-term optimal functioning of the engine and injectors, such deposits in the nozzle openings must be prevented or reduced using suitable fuel additives.

[0008] Deposits in the injection systems of modern diesel engines cause significant performance problems. It is widely recognized that such deposits in the spray channels can lead to reduced fuel flow and thus to power loss. Deposits at the injector tip, on the other hand, impair the optimal formation of fuel spray, resulting in impaired combustion and, consequently, higher emissions and increased fuel consumption. In contrast to these conventional, "external" deposit phenomena, "internal" deposits (collectively referred to as internal diesel injector deposits (IDID)) in certain parts of the injectors, such as the nozzle needle, control piston, valve piston, valve seat, control unit, and the guides of these components, are also increasingly causing performance problems. Conventional additives are ineffective against these IDIDs.

[0009] US Pat. No. 4,248,719 describes quaternized ammonium salts produced by reacting an alkenyl succinimide with a monocarboxylic acid ester. These salts are used as dispersants in lubricating oils to prevent sludge formation. In particular, the reaction of polyisobutylsuccinic anhydride (PIBSA) with N,N-dimethylaminopropylamine (DMAPA) and quaternization with methyl salicylate is described. However, it does not suggest any use in fuels, particularly diesel fuels. The use of PIBSA with low degrees of bismaleation (<20%) is not described.

[0010] US Pat. No. 4,171,959 describes quaternized ammonium salts of hydrocarbyl-substituted succinimides, which are suitable as detergent additives for gasoline compositions. Alkyl halides are preferably used for quaternization. Organic C 2 -C 8 hydrocarbyl carboxylates and sulfonates are also mentioned. Consequently, the quaternized ammonium salts provided according to the teaching therein have either a halide or a C 2 -C 8 hydrocarbyl carboxylate or a C 2 -C 8 hydrocarbyl sulfonate group as the counterion. The use of PIBSA with low degrees of bismaleation <20% is also not described therein.

[0011] EP-A-2 033 945 discloses cold flow improvers produced by quaternizing specific tertiary monoamines bearing at least one C 8 -C 40 alkyl radical with a C 1 -C 4 alkyl ester of specific carboxylic acids. Examples of such carboxylic acid esters are dimethyl oxalate, dimethyl maleate, dimethyl phthalate, and dimethyl fumarate. Applications other than improving the CFPP value of middle distillates are not documented in EP-A-2 033 945.

[0012] WO 2006 / 135881 describes quaternized ammonium salts prepared by condensing a hydrocarbyl-substituted acylating agent with an oxygen- or nitrogen-containing compound with a tertiary amino group, followed by quaternization using hydrocarbyl epoxide in combination with stoichiometric amounts of an acid, such as acetic acid. Other quaternizing agents claimed in WO 2006 / 135881 are dialkyl sulfates, benzyl halides, and hydrocarbyl-substituted carbonates, with dimethyl sulfate, benzyl chloride, and dimethyl carbonate being experimentally investigated.

[0013] However, the quaternizing agents preferably used in WO 2006 / 135881 have serious disadvantages, such as: toxicity or carcinogenicity (e.g. in the case of dimethyl sulfate and benzyl halides), no residue-free combustion (e.g. in the case of dimethyl sulfate and alkyl halides), and insufficient reactivity, which leads to incomplete quaternization or uneconomical reaction conditions (long reaction times, high reaction temperatures, excess of quaternizing agent; e.g. in the case of dimethyl carbonate).

[0014] EP-A-2 033 945 describes the preparation of halogen- and sulfur-free quaternary ammonium salts of organic carboxylic acids (such as oxalic acid, phthalic acid, salicylic acid, malonic acid and maleic acid and their alkyl esters) and their use to improve the CFPP value of diesel fuels.

[0015] Quaternary ammonium salts of alpha-hydroxycarboxylic acids are proposed in EP-A-1 254 889 as cleaning agents for electronic components.

[0016] Furthermore, Japanese patent application number 61-012197 describes the use of quaternary ammonium salts of organic carboxylic acids as a surfactant or raw material for medicines or cosmetics.

[0017] WO2012 / 004300 describes the production of quaternized nitrogen compounds by a. a compound containing at least one oxygen- or nitrogen-containing group reactive with the anhydride and additionally containing at least one quaternizable amino group is added to a polycarboxylic acid anhydride compound with opening of the anhydride ring and b. the addition product from step a) is quaternized, in particular with an epoxide without adding an H +< donor; as well as correspondingly produced quaternized nitrogen compounds with typical intramolecular betaine structure, fuels and lubricants and additive packages comprising such compounds, as well as various applications of these compounds.

[0018] The task was therefore to provide additional fuel additives that prevent deposits in the injector tip and internal injector deposits during operation of common rail diesel engines. Brief description of the invention:

[0019] It has now surprisingly been found that the above object is achieved by providing quaternized nitrogen compounds, such as hydrocarbylamine compounds or power compositions additives therewith.

[0020] Surprisingly, the additives according to the invention, as particularly illustrated by the enclosed application examples, are surprisingly effective in common rail diesel engines and are characterized by their particular suitability as an additive for reducing power loss due to external and cold start problems due to internal deposits. Character description:

[0021] Figure 1 shows the sequence of a one-hour engine test cycle according to CEC F-098-08. Figure 2A to D shows photographs of injectors of a DISI gasoline engine, operated with fuel, either unadditized (A) or additized with various additives according to the invention (B, C, D) Detailed description of the invention: A1) Special embodiments

[0022] The present invention particularly relates to the following specific embodiments: 1. A fuel composition comprising, in a major amount of a conventional fuel, a proportion, in particular an effective amount, of at least one reaction product comprising a quaternized nitrogen compound, wherein the reaction product is obtainable by reacting a quaternizable nitrogen compound, such as a quaternizable alkylamine, containing at least one quaternizable, in particular tertiary amino group, with a quaternizing agent that converts the at least one quaternizable, in particular tertiary amino group into a quaternary ammonium group, wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid. In particular, the fuel composition is selected from middle distillate, in particular diesel, and especially biodiesel fuel compositions.In particular, such middle distillate fuel compositions comprise a mixture of middle distillate fuel and biofuel oil. Furthermore, such middle distillate fuel compositions comprise, in particular, biofuel oil, in amounts of 1 to 30 wt. %, in particular 3 to 10 wt. %, based on the total amount of middle distillate of fossil, vegetable, or animal origin and biofuel oil; in particular based on alkyl esters of fatty acids; especially lower alkyl esters, in particular C 1 - to C 4 -alkyl esters, which are obtainable by transesterification of the glycerides, in particular triglycerides, occurring in vegetable and / or animal oils and / or fats using lower alcohols. In such middle distillate fuel compositions, the alkyl ester of fatty acid is, in particular, selected from sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME"), and in particular rapeseed oil methyl ester ("RME").Fuel or lubricant composition according to embodiment 1, wherein the quaternizable nitrogen compound is selected from a) at least one alkylamine, which comprises at least one compound of the following general formula 3, R a R b R c N (3) wherein at least one of the radicals R a , R b and R c , such asone or two represent a straight-chain or branched, saturated or unsaturated C 8 -C 40 hydrocarbyl radical (in particular straight-chain or branched C 8 -C 40 alkyl) and the remaining radicals represent identical or different, straight-chain or branched, saturated or unsaturated C 1 -C 6 hydrocarbyl radicals (in particular C 1 -C 6 alkyl); b) at least one polyalkene-substituted amine containing at least one quaternizable, in particular tertiary, amino group; c) at least one polyether-substituted amine containing at least one quaternizable, in particular tertiary, amino group; and d) at least one reaction product of a hydrocarbyl-substituted acylating agent and a compound containing a nitrogen or oxygen atom and additionally containing at least one quaternizable, in particular tertiary, amino group; and e) mixtures thereof; or 2a.Fuel composition according to embodiment 1, wherein the quaternizable nitrogen compound, e.g.is an alkylamine which comprises at least one compound of the following general formula 3, R a R b R c N (3) wherein all radicals R a , R b and R c are identical or different straight-chain or branched, saturated or unsaturated C 8 -C 40 hydrocarbyl radicals, in particular straight-chain or branched C 8 -C 40 alkyl radicals; or wherein the quaternizable nitrogen compound is selected from at least one alkylamine of the above general formula 3, wherein the radicals R a , R b and R c are identical or different short-chain alkyl radicals, in particular straight-chain or branched alkyl groups having 1 to 7 or in particular 1 to 4 carbon atoms; Furthermore, the quaternizable tertiary amine can in particular be selected from the group consisting of hydroxyalkyl-substituted primary, secondary, and in particular tertiary monoamines and hydroxyalkyl-substituted primary, secondary, and in particular tertiary diamines.Furthermore, the quaternizable tertiary amine can be a hydroxyalkyl-substituted monoamine selected from the group consisting of N-hydroxyalkyl monoamines, N,N-dihydroxyalkyl monoamines, and N,N,N-trihydroxyalkyl monoamines. Furthermore, the quaternizable tertiary amine can be selected from the group consisting of ethanolamine, 3-hydroxy-1-propylamine, diethanolamine, diisopropanolamine, N-(2-hydroxyethyl)ethylenediamine, triethanolamine, 1-(3-hydroxypropyl)imidazole, tris(hydroxymethyl)amine, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 2-dimethylamino-1-ethanol, and 4-diethylamino-1-butanol. 3. The fuel composition according to any of embodiments 1 and 2, wherein the quaternizing agent comprises an epoxide of the general formula 4. wherein the R d radicals present therein are identical or different and are H or a hydrocarbyl radical, wherein the hydrocarbyl radical is an aliphatic or aromatic radical having at least 1 to 10 carbon atoms and optionally additionally contains heteroatoms, such as in particular O, N, NH or S in its chain. 4. Fuel composition according to any one of embodiments 1 to 3, wherein the free acid of the quaternizing agent is a hydrocarbyl-substituted C 3 -C 28 dicarboxylic acid. 5. Fuel or lubricant composition according to any one of embodiments 1 to 4, wherein the hydrocarbyl substituent of the carboxylic acid has a number-average molecular weight (M n ) of 85 to 20,000 or is a polyalkylene radical with a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25. 6.A fuel composition according to any one of the preceding embodiments, wherein the quaternizable tertiary amine is a compound of the above general formula 3, wherein at least two of the radicals R a , R b , and R c are the same or different and represent a straight-chain or branched C 10 -C 20 alkyl radical, and the remaining radical represents C 1 -C 4 alkyl. 7. A fuel or lubricant composition according to any one of the preceding embodiments, wherein the quaternizing agent is selected from hydrocarbyl epoxides of the above general formula 4 in combination with a hydrocarbyl-substituted dicarboxylic acid, wherein in particular the carboxylic acid is selected from malonic, succinic, glutaric, adipic, and pimelic acid. 8.Fuel composition according to one of the preceding embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels, and alkanol-containing gasoline fuels, such as bioethanol-containing fuels, in particular diesel fuels.

[0023] Furthermore, the following embodiments 9 to 15 are described herein, but are not the subject of the invention: 9. A quaternized nitrogen compound as defined in any one of embodiments 1 to 7. 10. A process for preparing a quaternized nitrogen compound according to embodiment 9, comprising reacting a quaternizable alkylamine containing at least one quaternizable tertiary amino group with a quaternizing agent that converts the at least one tertiary amino group into a quaternary ammonium group, wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a hydrocarbyl-substituted polycarboxylic acid. 11. Use of a quaternized nitrogen compound according to embodiment 9 or prepared according to embodiment 10 as a fuel or lubricant additive. 12.Use according to embodiment 11 as an additive for reducing the fuel consumption of direct-injection diesel engines, in particular diesel engines with common rail injection systems, and / or for minimizing power loss in direct-injection diesel engines, in particular in diesel engines with common rail injection systems (as determined, for example, in a DW10 test based on CEC F-098-08, as described in more detail below in the experimental section). 13. Use according to embodiment 11 as a gasoline additive for reducing deposits in the intake system of a gasoline engine, such as, in particular, DISI and PFI (Port Fuel Injector) engines. 14. Use according to embodiment 10 as a diesel fuel additive for reducing and / or preventing deposits in the injection systems, such as, for example,determined in an XUD 9 test, according to CEC-F-23-1-01), such as in particular internal diesel injector deposits (IDID) and / or valve sticking in direct-injection diesel engines, in particular in common rail injection systems (as determined, for example, according to an IDID test procedure, as described in more detail below in the experimental section). 15. Additive concentrate comprising, in combination with other diesel or gasoline fuel additives or lubricant additives, at least one quaternized nitrogen compound as defined in embodiment 9 or produced according to embodiment 10. .

[0024] Further embodiments described herein, but which are not the subject of the invention, relate to: The use of a reaction product comprising a quaternized nitrogen compound or a partial fraction thereof obtained from the reaction product by purification and containing a quaternized nitrogen compound, wherein the reaction product is obtainable by Reaction of a quaternizable nitrogen compound containing at least one quaternizable, in particular tertiary amino group with a quaternizing agent that converts the at least one quaternizable, in particular tertiary amino group into a quaternary ammonium group, wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid; as a fuel or lubricant additive or kerosene additive.

[0025] In particular, such use is described as an additive for reducing the fuel consumption of direct-injection diesel engines, in particular diesel engines with common rail injection systems, and / or for minimizing the power loss in direct-injection diesel engines, in particular in diesel engines with common rail injection systems.

[0026] In particular, such use is described as a gasoline additive for reducing deposits in the intake system of a gasoline engine, such as in particular DISI and PFI (Port Fuel Injector) engines; or a use as a diesel fuel additive for reducing and / or preventing deposits in the injection systems, such as in particular Internal Diesel Injector Deposits (IDID) and / or valve sticking in direct-injection diesel engines, in particular in common rail injection systems.

[0027] In particular, such a use is described, wherein the quaternizable nitrogen compound is selected from: a) at least one alkylamine of the following general formula 3 R a R b R c N (3) wherein at least one of the radicals R a , R b and R c stands for a straight-chain or branched, saturated or unsaturated C 8 -C 40 hydrocarbyl radical (in particular straight-chain or branched C 8 -C 40 alkyl) and the remaining radicals stand for identical or different, straight-chain or branched, saturated or unsaturated C 1 -C 6 hydrocarbyl radicals (in particular C 1 -C 6 alkyl); or wherein all radicals R a , R b and R c stand for identical or different straight-chain or branched, saturated or unsaturated C 8 -C 40 hydrocarbyl radicals, in particular straight-chain or branched C 8 - C 40 alkyl radicals; b) at least one polyalkene-substituted amine containing at least one quaternizable, in particular tertiary, amino group; c) at least one polyether-substituted amine containing at least one quaternizable, in particular tertiary, amino group;and d) at least one reaction product of a hydrocarbyl-substituted acylating agent and a compound containing a nitrogen or oxygen atom and additionally containing at least one quaternizable amino group; and e) mixtures thereof.

[0028] In particular, such a use is described, wherein the quaternizing agent comprises an epoxide of the general formula 4 where the radicals R d contained therein are identical or different and represent H or a hydrocarbyl radical, where the hydrocarbyl radical represents an aliphatic or aromatic radical having 1 to 10 carbon atoms.

[0029] In particular, such a use is described, wherein the free acid of the quaternizing agent is a hydrocarbyl-substituted C 3 -C 28 dicarboxylic acid, wherein in particular the hydrocarbyl substituent of the carboxylic acid has a number-average molecular weight (M n ) of 85 to 20,000 or is a polyalkylene radical with a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25.

[0030] In particular, such a use is described, wherein the quaternizable tertiary amine is a compound of formula 3, wherein at least two of the radicals R a , R b and R c are the same or different and represent a straight-chain or branched, C 10 -C 20 -alkyl radical and the remaining radical represents C 1 -C 4 -alkyl.

[0031] In particular, such a use is described, wherein the quaternizing agent is selected from lower alkylene oxides in combination with a polyalkenyl-substituted dicarboxylic acid.

[0032] In particular, such a use is described, wherein the fuel is selected from diesel fuels, biodiesel fuels, gasoline fuels, and alkanol-containing gasoline fuels.

[0033] Suitable test methods for verifying the applications described above are known to the person skilled in the art or are described in the following experimental section, to which reference is hereby expressly made in general. A2) General definitions

[0034] Unless otherwise stated, the following general meanings apply: "Quaternizable" nitrogen groups or amino groups include in particular primary, secondary and, above all, tertiary amino groups.

[0035] "Hydrocarbyl" is broadly defined and includes both long-chain and short-chain, straight-chain, or branched hydrocarbon radicals with 1 to 50 carbon atoms, which may contain additional heteroatoms such as O, N, NH, or S. A special group of hydrocarbyl radicals includes both long-chain and short-chain, straight-chain, or branched alkyl radicals with 1 to 1000, 3 to 500, and 4 to 400 carbon atoms.

[0036] "Long-chain" or "high-molecular-weight" hydrocarbyl radicals represent straight-chain or branched hydrocarbon radicals and have 7 to 50, 8 to 50, 8 to 40, or 10 to 20 carbon atoms, which may optionally contain additional heteroatoms, such as O, N, NH, or S, in their chain. Furthermore, the radicals may be mono- or polyunsaturated and contain one or more non-cumulative, such as 1 to 5, such as 1, 2, or 3 CC double bonds or CC triple bonds, in particular 1, 2, or 3 double bonds. They may be of natural or synthetic origin.

[0037] They can also have a number-average molecular weight (M n ) of 85 to 20,000, such as 113 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500. They are then composed in particular essentially of C 2-6 , in particular C 2-4 monomer units, such as ethylene, propylene, n- or isobutylene or mixtures thereof, where the various monomers can be randomly distributed or polymerized in as blocks. Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or poly-C 2-6 or poly-C 2-4 alkylene radicals. Suitable long-chain hydrocarbyl radicals and their preparation are also described, for example, in WO2006 / 135881 and the literature cited therein.

[0038] Examples of particularly useful polyalkylene radicals are polyisobutenyl radicals derived from so-called "highly reactive" polyisobutenes, which are characterized by a high content of terminal double bonds. Terminal double bonds are alpha-olefinic double bonds of the type which together are also referred to as vinylidene double bonds. Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, in particular greater than 80 mol% or greater than 85 mol%. Polyisobutenes which have uniform polymer backbones are particularly preferred. Uniform polymer backbones are particularly those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight of isobutene units. Such highly reactive polyisobutenes preferably have a number-average molecular weight in the above-mentioned range. In addition, the highly reactive polyisobutenes can have a polydispersity in the range from 1.05 to 7, in particular from about 1.1 to 2.5, such as less than 1.9 or less than 1.5.Polydispersity is the quotient of the weight-average molecular weight Mw divided by the number-average molecular weight Mn.

[0039] Particularly suitable highly reactive polyisobutenes include the Glissopal brands from BASF SE, in particular Glissopal 1000 (Mn = 1000), Glissopal V 33 (Mn = 550), and Glissopal 2300 (Mn = 2300), and their blends. Other number-average molecular weights can be achieved in a manner known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes in specific molecular weight ranges.

[0040] A special group of long-chain hydrocarbyl radicals includes straight-chain or branched alkyl radicals ("long-chain" alkyl radicals") having 8 to 50, such as 8 to 40 or 8 to 30 or 10 to 20 carbon atoms.

[0041] Another group of special long-chain hydrocarbyl radicals comprises polyalkylene radicals which are composed in particular essentially of C 2-6 -, in particular C 2-4 -monomer units, such as ethylene, propylene, n- or iso-butylene or mixtures thereof and have a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25.

[0042] "Short-chain hydrocarbyl" or "low molecular weight hydrocarbyl" particularly represents straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, such as 2, 3 or 4, heteroatom groups, such as -O- or -NH-, or optionally mono- or polysubstituted, such as 2, 3 or 4-fold.

[0043] "Hydrocarbylene" stands for straight-chain or singly or multiply branched bridging groups having 1 to 10 carbon atoms, optionally interrupted by one or more, such as 2, 3 or 4, heteroatom groups, such as -O- or -NH-, or optionally mono- or polysubstituted, such as 2, 3 or 4-fold.

[0044] "Alkyl" or "lower alkyl" stands in particular for saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 5, 1 to 6, or 1 to 7 carbon atoms, such as. B. Methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, n-hexyl, 1,1-Dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; as well as n-heptyl, and the singly or multiply branched analogues thereof.

[0045] "Long-chain alkyl" stands for example for saturated, straight-chain or branched hydrocarbon radicals having 8 to 50, such as 8 to 40 or 8 to 30 or 10 to 20 carbon atoms, such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, constitutional isomers, in particular singly or multiply branched isomers and higher homologues thereof.

[0046] "Hydroxyalkyl" stands in particular for the mono- or polyhydroxylated, in particular singly hydroxylated analogues of the above alkyl radicals, such as the monohydroxylated analogues of the above straight-chain or branched alkyl radicals, such as the linear hydroxyalkyl groups, such as those with a primary (terminal) hydroxyl group, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, or those with non-terminal hydroxyl groups, such as 1-hydroxyethyl, 1- or 2-hydroxypropyl, 1- or 2-hydroxybutyl or 1-, 2- or 3-hydroxybutyl.

[0047] "Alkenyl" stands for mono- or polyunsaturated, in particular monounsaturated, straight-chain or branched hydrocarbon radicals with 2 to 4, 2 to 6, or 2 to 7 carbon atoms and a double bond in any position, e.g. B. C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1-Methyl-1-butenyl, 2-Methyl-1-butenyl, 3-Methyl-1-butenyl, 1-Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2-butenyl, 1-Methyl-3-butenyl, 2-methyl-3-butenyl, 3-Methyl-3-butenyl, 1,1-Dimethyl-2-propenyl, 1,2-Dimethyl-1-propenyl, 1,2-Dimethyl-2-propenyl, 1-Ethyl-1-propenyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-Methyl-3-pentenyl, 2-Methyl-3pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pentenyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1,1-Dimethyl-2-butenyl, 1,1-Dimethyl-3-butenyl, 1,2-Dimethyl-1-butenyl, 1,2-Dimethyl-2-butenyl, 1,2-Dimethyl-3-butenyl, 1,3-Dimethyl-1-butenyl, 1,3-Dimethyl-2-butenyl, 1,3-Dimethyl-3-butenyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3-Dimethyl-1-butenyl, 3,3-Dimethyl-2-butenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 2-Ethyl-1-butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Ethyl-1-methyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl und 1-Ethyl-2-methyl-2-propenyl.,

[0048] " Hydroxyalkenyl" steht insbesondere für die ein- oder mehrfach, insbesondere einfach hydroxylierten Analoga obiger Alkenylreste

[0049] "Aminoalkyl" and "aminoalkenyl" stand in particular for the mono- or polyamino, in particular singly aminated analogues of the above alkyl or alkenyl radicals, or analogues of the above hydroxyalkyl, wherein the OH group is replaced by an amino group.

[0050] "Alkylene" stands for straight-chain or singly or multiply branched hydrocarbon bridging groups having 1 to 10 carbon atoms, such as C 1 -C 7 -alkylene groups selected from -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -,-(CH 2 ) 4 -, -(CH 2 ) 2 -CH(CH 3 )-, -CH 2 -CH(CH 3 )-CH 2 -, (CH 2 ) 4 -, -(CH 2 ) 5 -, -(CH 2 ) 6 , -(CH 2 ) 7 -, -CH(CH 3 )-CH 2 -CH 2 -CH(CH 3 )- or - CH(CH 3 )-CH 2 -CH 2 -CH 2 -CH(CH 3 )- or C 1 -C 4 -alkylene groups selected from -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -,-(CH 2 ) 4 -, -(CH 2 ) 2 -CH(CH 3 )-, -CH 2 -CH(CH 3 )-CH 2 - or for C 2 -C 6 -alkylene groups, such as

[0051] -CH 2 -CH(CH 3 )-, -CH(CH 3 )-CH 2 -, -CH(CH 3 )-CH(CH 3 )-, -C(CH 3 ) 2 -CH 2 -, -CH 2 -C(CH 3 ) 2 -, -C(CH 3 ) 2 -CH(CH 3 )-, -CH(CH 3 )-C(CH 3 ) 2 -, -CH 2 -CH(Et)-, -CH(CH 2 CH 3 )-CH 2 -, -CH(CH 2 CH 3 )-CH(CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -CH 2 -, -CH 2 -C(CH 2 CH 3 ) 2 -, -CH 2 -CH(n-propyl)-, -CH(n-propyl)-CH 2 -, -CH(n-Propyl)-CH(CH 3 )-, -CH 2 -CH(n-Butyl)-, -CH(n-Butyl)-CH 2 -, -CH(CH 3 )-CH(CH 2 CH 3 )-, -CH(CH 3 )-CH(n-Propyl)-, -CH(CH 2 CH 3 )-CH(CH 3 )-, -CH(CH 3 )-CH(CH 2 CH 3 )-, or for C 2 -C 4 -alkylene groups, such as selected from -(CH 2 ) 2 -, -CH 2 -CH(CH 3 )-, -CH(CH 3 )-CH 2 -, -CH(CH 3 )-CH(CH 3 )-, -C(CH 3 ) 2 -CH 2 -, -CH 2 -C(CH 3 ) 2 -, -CH 2 -CH(CH 2 CH 3 )-, -CH(CH 2 CH 3 )-CH 2 -,

[0052] "Oxyalkylene radicals correspond to the above definition of straight-chain or singly or multiply branched alkylene radicals having 2 to 10 carbon atoms, where the carbon chain is interrupted once or multiple times, in particular once, by an oxygen heteroatom. Non-limiting examples are: -CH 2 -O-CH 2 -, -(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 ) 3 -O-(CH 2 ) 3 -, or -CH 2 -O-(CH 2 ) 2 -, -(CH 2 ) 2 -O-(CH 2 ) 3 -, -CH 2 -O-(CH 2 ) 3

[0053] "Aminoalkylene" correspond to the above definition of straight-chain or singly or multiply branched alkylene radicals having 2 to 10 carbon atoms, where the carbon chain is interrupted once or multiple times, in particular once, by a nitrogen group (especially an NH group). Non-limiting examples include: -CH 2 -NH-CH 2 -, - (CH 2 ) 2 -NH-(CH 2 ) 2 -, -(CH 2 ) 3 -NH-(CH 2 ) 3 -, or -CH 2 -NH-(CH 2 ) 2 -, -(CH 2 ) 2 -NH-(CH 2 ) 3 -, - CH 2 -NH-(CH 2 ) 3 .

[0054] "Alkenylene" stands for the mono- or polyunsaturated, in particular monounsaturated analogues of the above alkylene groups having 2 to 10 carbon atoms, in particular for C 2 -C 7 -alkenylenes or C 2 -C 4 -alkenylene, such as -CH=CH-, -CH=CH-CH 2 -, - CH 2 -CH=CH-, -CH=CH-CH 2 -CH 2 -, -CH 2 -CH=CH-CH 2 -, -CH 2 -CH 2 -CH=CH-, -CH(CH 3 )-CH=CH-, -CH 2 -C(CH 3 )=CH-,

[0055] -"Cycloalkyl" stands for carbocyclic radicals having 3 to 20 carbon atoms, such as C 3 -C 12 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl, cycloheptyl, and cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or C 3 -C 7 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylethyl, cyclohexylmethyl, where the bond to the rest of the molecule can be made via any suitable C atom.

[0056] "Cycloalkenyl" or mono- or polyunsaturated cycloalkyl" stands in particular for monocyclic, mono- or polyunsaturated hydrocarbon groups having 5 to 8, preferably up to 6 carbon ring members, such as the monounsaturated radicals cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl;

[0057] "Aryl" stands for mono- or polynuclear, preferably mono- or dinuclear, optionally substituted aromatic radicals having 6 to 20, such as 6 to 10, ring carbon atoms, such as phenyl, biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyl, fluorenyl, indenyl, and phenanthrenyl. These aryl radicals may optionally bear 1, 2, 3, 4, 5, or 6 identical or different substituents.

[0058] "Alkylaryl" stands for the analogues of the above aryl radicals which are mono- or polysubstituted, in particular mono- or di-alkyl-substituted, in any ring position, where aryl also has the meanings given above, such as C 1 -C 4 -alkyl-phenyl-, where the C 1 -C 4 -alkyl radicals can be in any ring position.

[0059] "Substituents" for radicals indicated herein are, in particular, unless otherwise stated, selected from keto groups, - COOH, -COO-alkyl, - OH, -SH, -CN, amino, -NO 2 , alkyl, or alkenyl groups.

[0060] "Mn" stands for the number-average molecular weight and is determined in a conventional manner; in particular, such information refers to Mn values ​​determined by relative methods, such as gel permeation chromatography using THF as eluent and polystyrene standards, or absolute methods, such as vapor phase osmometry using toluene as solvent.

[0061] "Mw" stands for the weight-average molecular weight and is determined in a conventional manner; in particular, such information refers to Mw values ​​determined by relative methods, such as gel permeation chromatography with THF as eluent and polystyrene standards, or absolute methods, such as light scattering.

[0062] The "degree of polymerization" usually refers to the numerical average degree of polymerization (determination method: gel permeation chromatography with THF as eluent and polystyrene standards; or GC-MS coupling). A3) Quaternizable nitrogen compounds

[0063] Quaternizable nitrogen compounds include: A3.1) Tertiary amines

[0064] Tertiary amines are in particular compounds of the above formula (3) and are known compounds per se, as described, for example, in EP-A-2 033 945.

[0065] The tertiary amine starting material (3) preferably carries a segment of the formula NR a R b where one of the radicals has an alkyl group having 8 to 40 carbon atoms and the other has an alkyl group having up to 40, particularly preferably 8 to 40, carbon atoms. The radical R c is in particular a short-chain C 1 -C 6 alkyl radical, such as a methyl, ethyl or propyl group. R a and R b can be straight-chain or branched, and / or can be the same or different. For example, R a and R b can be a straight-chain C 12 -C 24 alkyl group. Alternatively, only one of the two radicals can be long-chain (e.g. having 8 to 40 carbon atoms) and the other can be a methyl, ethyl or propyl group.

[0066] The segment NR a R b is advantageously derived from a secondary amine, such as dioctadecylamine, di-coconut amine, dihydrogenated tallow amine, and methylbehenylamine. Amine mixtures such as those obtainable from natural materials are also suitable. For example, a secondary hydrogenated tallow amine, wherein the alkyl groups are derived from hydrogenated tallow fat and contain approximately 4 wt.% C 14 , 31 wt.% C 16 , and 59 wt.% C 18 alkyl groups, can be mentioned. Corresponding tertiary amines of formula (3) are marketed, for example, by Akzo Nobel under the names Armeen ®< M2HT or Armeen ®< M2C.

[0067] However, the tertiary amine starting material (3) can also be designed in such a way that the radicals R a , R b and R c have identical or different long-chain alkyl radicals, in particular straight-chain or branched alkyl groups having 8 to 40 carbon atoms.

[0068] However, the tertiary amine starting material (3) can also be formed such that the radicals R a , R b and R c have identical or different short-chain alkyl radicals, in particular straight-chain or branched alkyl groups having 1 to 7 or in particular 1 to 4 carbon atoms.

[0069] Further non-limiting examples of suitable amines are: N,N-dimethyl-N-(2-ethylhexyl)amine, N,N-dimethyl-N-(2-propylheptyl)amine, dodecyldimethylamine, hexadecyldimethylamine, oleyldimethylamine, stearyldimethylamine, heptadecyldimethylamine, cocoyldimethylamine, dicocoylmethylamine, tallow dimethylamine, ditallow methylamine, tridodecylamine, trihexadecylamine, trioctadecylamine, soy dimethylamine, tris(2-ethylhexyl)amine, and Alamine 336 (tri-n-octylamine).

[0070] Non-limiting examples of short-chain tertiary amines are: trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, ethyldimethylamine, dimethylethylamine, n-propyldimethylamine, isopropyldimethylamine, n-propyldiethylamine, isopropyldiethylamine, n-butyldimethylamine, n-butyldiethylamine, n-butyldipropylamine.

[0071] Short-chain triamines are particularly useful when the quaternizing agent (see below) carries one or more alkyl radicals R d with more than one C atom or one or more aromatic radicals R d

[0072] A3.2) Quaternizable, polyether-substituted amine containing at least one quaternizable, in particular tertiary, amino group;

[0073] Such compounds are described, for example, in the applicant's WO2013 / 064689, to which reference is hereby expressly made.

[0074] Such substituted amines have in particular at least one, in particular a polyether substituent with monomer units of the general formula Ic -[-CH(R 3 )-CH(R 4 )-O-]- (Ic) wherein R 3 and R 4 are the same or different and represent H, alkyl, alkylaryl or aryl.

[0075] The polyether-substituted amine can have a number-average molecular weight in the range of 500 to 5000, in particular 800 to 3000 or 900 to 1500.

[0076] The quaternizable, polyether-substituted amines are in particular nitrogen compounds of the general formula Ia-1 or Ib-2 wherein R 1 and R 2 are the same or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together are alkylene, oxyalkylene or aminoalkylene; R 3 and R 4 are the same or different and are H, alkyl, alkylaryl or aryl; R 6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example by at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom; A is a straight-chain or branched alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S; and n is an integer value from 1 to 50;

[0077] In particular, nitrogen compounds of the formulas Ia-1 and Ib-2 are to be mentioned, in which R 1 and R 2 are the same or different and are C 1 -C 6 alkyl, hydroxy-C 1 -C 6 alkyl, hydroxy-C 1 -C 6 alkenyl, or amino-C 1 -C 6 alkyl, or R 1 and R 2 together form a C 2 -C 6 alkylene, C 2 -C 6 oxyalkylene or C 2 -C 6 aminoalkylene radical; R 3 and R 4 are the same or different and are H, C 1 -C 6 alkyl or phenyl; R 6 is C 1 -C 20 alkyl, such as C 10 -C 20 , C 11 -C 20 or C 12 -C 20 alkyl or aryl or alkylaryl, where alkyl is in particular C 1 -C 20 ; A represents a straight-chain or branched C 2 -C 6 alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S; and n represents an integer value from 1 to 30.

[0078] Also particularly noteworthy are reaction products of N,N-dimethylethanolamine and propylene oxide as described in Synthesis Example 1 of WO 2013 / 064689. This reaction can also be carried out uncatalyzed or with an amine (e.g., imidazole) as a catalyst, as described, for example, in M. Ionescu, Chemistry and Technology of Polyols for Polyurethanes, 2005, ISBN 978-85957-501-7.

[0079] Nitrogen compounds of the general formula la-1 can be prepared by reacting an aminoalkanol of the general formula II (R 1 )(R 2 )NA-OH (II) wherein R 1 , R 2 and A have the meanings given above, with an epoxide of the general formula III wherein R 3 and R 4 have the meanings given above, to give an alkoxylated amine of the formula wherein R 1 to R 4 , A and n have the meanings given above.

[0080] Nitrogen compounds of the general formula la-2 can be prepared by reacting an alcohol of the general formula V R 6 -OH (V) wherein R 6 has the meanings given above, with an epoxide of the general formula III wherein R 3 and R 4 have the meanings given above, to obtain a polyether of formula lb-1; wherein R 3 , R 4 and R 6 , A and n have the meanings given above and b) subsequently aminating the polyether of formula Ib-1 thus obtained with an amine of the general formula NH(R 1 )(R 2 ) (VII) wherein R 1 and R 2 have the meanings given above, to obtain an amine of formula Ib-2.

[0081] Starting compounds for the preparation of the above polyether-substituted, quaternizable nitrogen compounds are: 1) Alcohols such as, for example, of the general formula V R 6 -OH (V) in which R 6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, each optionally substituted, for example with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom; and 2) aminoalkanols such as, for example, of the general formula II (R 1 )(R 2 )NA-OH (II) in which R 1 and R 2 are the same or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together are alkylene, oxyalkylene or aminoalkylene; and A is a straight-chain or branched alkylene or alkenylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;

[0082] Another suitable group of quaternizable amino alcohols includes compounds selected from hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group and at least one hydroxyl group which can be linked to a polyether radical.

[0083] In particular, the quaternizable nitrogen compounds are selected from hydroxyalkyl-substituted primary, secondary, and especially tertiary monoamines and hydroxyalkyl-substituted primary, secondary, and especially tertiary diamines.

[0084] Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those which are provided with at least one, such as 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituted group.

[0085] Examples of "hydroxyalkyl-substituted monoamines" include: N-hydroxyalkyl monoamines, N,N-dihydroxyalkyl monoamines, and N,N,N-trihydroxyalkyl monoamines, where the hydroxyalkyl groups are identical or different and are also defined as above. Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl, or 4-hydroxybutyl.

[0086] Examples of "hydroxyalkyl-substituted polyamines" and especially "hydroxyalkyl-substituted diamines" include (N-hydroxyalkyl)alkylenediamines and N,N-dihydroxyalkylalkylenediamines, where the hydroxyalkyl groups are identical or different and are also defined as above. Hydroxyalkyl represents, in particular, 2-hydroxyethyl, 3-hydroxypropyl, or 4-hydroxybutyl; Alkylene represents, in particular, ethylene, propylene, or butylene.

[0087] The following quaternizable nitrogen compounds are particularly worth mentioning: NAME FORMULA Alcohols with primary and secondary amine Ethanolamine 3-Hydroxy-1-propylamine Diethanolamine Diisopropanolamin N-(2-Hydroxyethyl)ethylenediamine Alcohols with tertiary amine Triethanolamine, (2.2 I<,2 II<-nitrilotriethanol) 1-(3-Hydroxypropyl)imidazol Tris(hydroxymethyl)amine 3-Dimethylamino-1-propanol 3-Diethylamino-1-propanol 2-Dimethylamino-1-ethanol 4-Diethylamino-1-butanol

[0088] The polyether-substituted quaternizable compounds (Ia-1 and Ib-1) can be prepared as follows: a1) Starting from amino alcohols of formula II:

[0089] The amino alcohols of the general formula II can be alkoxylated in a manner known in principle, whereby alkoxylated amines of the general formula Ia-1 are obtained.

[0090] The procedure for conducting alkoxylations is known in principle to those skilled in the art. It is also known to those skilled in the art that the molecular weight distribution of the alkoxylates can be influenced by the reaction conditions, in particular the choice of catalyst.

[0091] C 2 - C 16 alkylene oxides, such as ethylene oxide, propylene oxide, or butylene oxide, are used for the alkoxylation. 1,2-Alkylene oxides are preferred.

[0092] The alkoxylation can be a base-catalyzed alkoxylation. For this purpose, the amino alcohols (II) can be treated with alkali metal hydroxides, preferably potassium hydroxide, or with alkali metal alkoxides such as sodium methylate in a pressure reactor. Any water still present in the mixture can be removed by reducing the pressure (e.g. <100 mbar) and / or increasing the temperature (30 to 150°C). The alcohol is then present as the corresponding alkoxide. The mixture is then rendered inert with an inert gas (e.g. nitrogen), and the alkylene oxide(s) are added stepwise at temperatures of 60 to 180°C up to a pressure of max. 10 bar. At the end of the reaction, the catalyst can be neutralized by adding acid (e.g. acetic acid or phosphoric acid) and can be filtered off if necessary. The basic catalyst can also be neutralized by adding commercially available magnesium silicates, which are then filtered off.Optionally, the alkoxylation can also be carried out in the presence of a solvent. This can be, for example, toluene, xylene, dimethylformamide, or ethylene carbonate.

[0093] However, the alkoxylation of the amino alcohols can also be carried out using other methods, for example by acid-catalyzed alkoxylation. Furthermore, double hydroxide clays as described in DE 43 25 237 A1 can be used, or double metal cyanide catalysts (DMC catalysts) can be used. Suitable DMC catalysts are disclosed, for example, in DE 102 43 361 A1, in particular sections

[0029] to

[0041] , and the literature cited therein. For example, Zn-Co type catalysts can be used. To carry out the reaction, the amino alcohol can be admixed with the catalyst, the mixture can be dehydrated as described above, and reacted with the alkylene oxides as described. Typically, no more than 1000 ppm of catalyst are used with respect to the mixture, and the catalyst can remain in the product due to this small amount.The amount of catalyst can usually be less than 1000 ppm, for example 250 ppm and less.

[0094] Alternatively, the alkoxylation can also be carried out by reacting the compounds (IV) and (V) with cyclic carbonates such as ethylene carbonate. a2) Starting from alkanols of formula V:

[0095] As described in the previous section a1) for amino alcohols (II), alkanols R 6 OH can also be alkoxylated analogously in a manner known in principle to give polyethers (Ib-1). The polyethers thus obtained can then be converted into the corresponding polyetheramines (Ib-2) by reductive amination with ammonia, primary amines or secondary amines (VII) by conventional methods in continuous or batch processes using hydrogenation or amination catalysts customary for this purpose, such as, for example, those containing catalytically active components based on the elements Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Re, Al, Si, Ti, Zr, Nb, Mg, Zn, Ag, Au, Os, Ir, Cr, Mo, W or combinations of these elements with one another, in customary amounts. The reaction can be carried out without solvent or, at high polyether viscosities, in the presence of a solvent, preferably in the presence of branched aliphatics such as isododecane.The amine component (VII) is generally used in excess, e.g., in a 2- to 100-fold excess, preferably a 10- to 80-fold excess. The reaction is carried out at pressures of 10 to 600 bar over a period of 10 minutes to 10 hours. After cooling, the catalyst is separated by filtration, excess amine component (VII) is evaporated, and the water of reaction is distilled off azeotropically or under a gentle stream of nitrogen.

[0096] If the resulting polyetheramine (Ib-2) contains primary or secondary amine functionalities (R 1 and / or R 2 are H), it can subsequently be converted into a polyetheramine with a tertiary amine function (R 1 and R 2 are not H). Alkylation can be carried out in a manner known in principle by reaction with alkylating agents. Suitable alkylating agents include, in principle, all alkylating agents, such as, for example, alkyl halides, alkylaryl halides, dialkyl sulfates, alkylene oxides, optionally in combination with acid; aliphatic or aromatic carboxylic acid esters, such as, in particular, dialkyl carboxylates; alkanoates; cyclic non-aromatic or aromatic carboxylic acid esters; dialkyl carbonates; and mixtures thereof. The reactions to the tertiary polyetheramine can also take place by reductive amination by reaction with a carbonyl compound, such as, for example, formaldehyde, in the presence of a reducing agent.Suitable reducing agents are formic acid or hydrogen in the presence of a suitable heterogeneous or homogeneous hydrogenation catalyst. The reactions can be carried out without solvents or in the presence of solvents. Suitable solvents include, for example, H2O, alkanols such as methanol or ethanol, or 2-ethylhexanol, aromatic solvents such as toluene, xylene or solvent mixtures of the Solvesso series, or aliphatic solvents, in particular mixtures of branched aliphatic solvents. The reactions are carried out at temperatures from 10°C to 300°C and pressures from 1 to 600 bar over a period of 10 minutes to 10 hours. The reducing agent is used at least stoichiometrically, preferably in excess, in particular in a 2- to 10-fold excess.

[0097] The resulting reaction product (polyetheramine Ib-1 or Ib-2) can theoretically be further purified or the solvent removed. However, this is usually not necessary, so the reaction product can be transferred to the next synthesis step, quaternization, without further purification. A3.3) Polyalkene-substituted amines with at least one tertiary, quaternizable nitrogen group

[0098] Also suitable as quaternizable nitrogen compounds are polyalkene-substituted amines having at least one tertiary nitrogen group. This group of compounds is also known and is described, for example, in WO 2008 / 060888 or US 2008 / 0113890 and the further prior art cited therein, which is hereby expressly incorporated by reference.

[0099] Such polyalkene-substituted amines having at least one tertiary amino group are derivable from an olefin polymer and an amine such as ammonia, monoamines, polyamines, or mixtures thereof. They can be prepared by a variety of processes, such as the following exemplary processes: One process for preparing a polyalkene-substituted amine comprises reacting a halogenated olefin polymer with an amine, as described in U.S. Patents 3,275,554, 3,438,757, 3,454,555, 3,565,804, 3,755,433, and 3,822,289.

[0100] Another process for preparing a polyalkene-substituted amine comprises reacting a hydroformylated olefin with a polyamine and hydrogenating the reaction product, as described in US 5,567,845 and 5,496,383

[0101] Another method for preparing a polyalkene-substituted amine comprises converting a polyalkene into the corresponding epoxide using a conventional epoxidizing reagent with or without a catalyst and converting the epoxide to the polyalkene-substituted amine by reaction with ammonia or an amine under reductive animation conditions, as described in US 5,350,429.

[0102] Another method for preparing polyalkene-substituted amines involves the hydrogenation of a β-aminonitrile prepared by reacting an amine with a nitrile, as described in US 5,492,641.

[0103] Another process for preparing a polyalkene-substituted amine comprises hydroformylating a polybutene or polyisobutylene with a catalyst such as rhodium or cobalt in the presence of CO and hydrogen at elevated pressures and temperatures, as described in US 4,832,702.

[0104] In one embodiment of the invention, the polyalkenes used for preparation are derived from olefin polymers. The olefin polymers may include homopolymers and copolymers of polymerizable olefin monomers having 2 to about 16 carbon atoms, 2 to about 6 carbon atoms, or 2 to about 4 carbon atoms.

[0105] Interpolymers are those in which two or more olefin monomers are interpolymerized by known conventional methods to produce polyalkenes having units within their structure derived from each of the two or more olefin monomers.

[0106] Thus, "interpolymers" include copolymers, terpolymers, and tetrapolymers.

[0107] "Polyalkenes", from which the polyalkene-substituted amines are derived, are also commonly referred to as "polyolefins".

[0108] The olefin monomers from which the olefin polymers are derived are polymerizable olefin monomers having one or more ethylenically unsaturated groups (i.e. >C=C< ), that is, they are monoolefinic monomers such as ethylene, propylene, 1-butene, isobutene (2-methyl-1-butene), 1-octene or polyolefinic monomers (usually diolefinic monomers) such as 1,3-butadiene and isoprene.

[0109] The olefin monomers are usually polymerizable terminal olefins, i.e., olefins that have the group > C=CH 2 in their structure. However, polymerizable internal olefin monomers can also be used, which are characterized by groups of the formula >CC=CC<

[0110] Specific examples of terminal and internal olefin monomers that can be used to prepare the polyalkenes by conventional methods are: ethylene, propylene, the butenes (butylene), especially 1-butene, 2-butene and isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 2-pentene, propylene tetramer, diisobutylene, isobutylene trimer, 1,2-butadiene, 1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,5-hexadiene, 2-methyl-5-propyl-1-hexene, 3-pentene, 4-octene and 3, 3-Dimethyl-1-pentene.

[0111] In another embodiment, the olefin polymer can be prepared by polymerizing a C 4 refinery stream having a butene content of about 35 to about 75 weight percent and an isobutene content of about 30 to about 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes typically contain predominantly (more than about 80% of the total repeat units) isobutene repeat units of the type (-CH 2 -C(CH 3 ) 2 -)

[0112] In another embodiment, the polyalkene substituent of the polyalkene-substituted amine is derived from a polyisobutylene.

[0113] In another embodiment, the amines that can be used to form the polyalkene-substituted amine include ammonia, monoamines, polyamines, or mixtures of that, including mixtures of various monoamines, mixtures of various polyamines, and mixtures of monoamines and polyamines (the diamines). The amines include aliphatic, aromatic, heterocyclic, and carbocyclic amines. Monoamines and polyamines are characterized by the presence of at least one HN group in their structure. The amines can be aliphatic, cycloaliphatic, aromatic, or heterocyclic.

[0114] The monoamines are generally substituted by a hydrocarbon group containing 1 to 50 carbon atoms. These hydrocarbon groups can, in particular, be aliphatic and free of acetylenically unsaturated groups and have 1 to about 30 carbon atoms. Particularly suitable are saturated aliphatic hydrocarbon radicals containing 1 to 30 carbon atoms.

[0115] In another embodiment, the monoamines may have the formula HNR 1 R 2 , where R 1 is a hydrocarbon group having up to 30 carbon atoms and R 2 is hydrogen or a hydrocarbyl group of up to about 30 carbon atoms. Examples of suitable monoamines are methylamine, ethylamine, diethylamine, 2-ethylhexylamine, di-(2-ethylhexyl)amine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine, and oleylamine.

[0116] Aromatic monoamines are those monoamines in which one carbon atom of the aromatic ring structure is directly bonded to the amine nitrogen atom. The aromatic ring will usually be a mononuclear aromatic ring (i.e., derived from benzene), but may contain fused aromatic rings, particularly those derived from naphthalene. Examples of aromatic monoamines are aniline, di(para-methylphenyl)amine, naphthylamine, and N-(n-butyl)aniline. Examples of aliphatic-substituted, cycloaliphatic-substituted, and heterocyclic-substituted aromatic monoamines are para-dodecylaniline, cyclohexyl-substituted naphthylamine, and thienyl-substituted aniline.

[0117] Hydroxyamines are also suitable monoamines. Such compounds are the hydroxyhydrocarbyl-substituted analogues of the aforementioned monoamines.

[0118] In one embodiment, the hydroxy monoamines may be of the formula HNR 3 R 4 , wherein R 3 represents a hydroxy-substituted alkyl group having up to about 30 carbon atoms, and in one embodiment, up to about 10 carbon atoms; and R 4 represents a hydroxy-substituted alkyl group having up to about 30 carbon atoms, hydrogen, or a hydrocarbyl group having up to about 10 carbon atoms. Examples of hydroxy-substituted monoamines include: ethanolamine, di-3-propanolamine, 4-hydroxybutylamine, diethanolamine, and N-methyl-2-hydroxypropylamine.

[0119] In another embodiment, the amine of the polyalkene-substituted amines can be a polyamine. The polyamine can be aliphatic, cycloaliphatic, heterocyclic, or aromatic. Examples of polyamines include: alkylene polyamines, hydroxy-containing polyamines, aryl polyamines, and heterocyclic polyamines.

[0120] The alkylene polyamines include those of the following formula HN(R 5< )-(Alkylene-N(R 5< )) n -(R 5< ) wherein n ranges from 1 to about 10, such as from 2 to about 7, or from 2 to about 5, and the "alkylene" group has from 1 to about 10 carbon atoms, such as from 2 to about 6, or from 2 to about 4 carbon atoms; the radicals R 5< independently represent hydrogen, an aliphatic group, a hydroxyl- or amine-substituted aliphatic group, each containing up to about 30 carbon atoms. Typically, R 5< represents H or lower alkyl (an alkyl group having from 1 to about 5 carbon atoms), especially H. Such alkylenepolyamines include: methylenepolyamines, ethylenepolyamines, butylenepolyamines, propylenepolyamines, pentylenepolyamines, hexylenepolyamines, and heptylenepolyamines. The higher homologs of such amines and related aminoalkyl-substituted piperazines are also included.

[0121] Specific alkylene polyamines for preparing the polyalkene-substituted amines are the following: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, 3-dimethylaminopropylamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, di(heptamethylene)triamine, tripropylenetetramine, pentaethylenehexamine, di(trimethylenetriamine), N-(2-aminoethyl)piperazine and 1,4-bis-(2-aminoethyl)piperazine.

[0122] Ethylene polyamines, such as those mentioned above, are particularly suitable for reasons of cost and effectiveness. Such polyamines are described in detail in the chapter "Diamines and Higher Amines" in the Encyclopedia of Chemical Technology, Second Edition, Kirk-Othemer, Volume 7, pages 27-39, Interscience Publishers, Division of John Wiley & Sons, 1965. Such compounds are most conveniently prepared by reacting an alkylene chloride with ammonia or by reacting an ethylene imine with a ring-opening reagent such as ammonia. These reactions lead to the production of complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines.

[0123] Other suitable types of polyamine mixtures are the products formed as residues by stripping the polyamine mixtures described above and often referred to as "polyamine bottoms." Generally, alkylene polyamine bottoms are those containing less than two, usually less than 1, weight percent of material boiling below about 200°C. A typical example of such ethylene polyamine bottoms are products designated "E-100" from Dow Chemical Company in Freeport, Texas. These alkylene polyamine bottoms include cyclic condensation products such as piperazine and higher analogues of diethylenetriamine, triethylenetetramine, and the like.

[0124] Hydroxyl-containing polyamines include hydroxyalkylalkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms. Such polyamines can be prepared by reacting the above-described alkylene polyamines with one or more alkylene oxides (e.g., ethylene oxide, propylene oxide, and butylene oxide). Similar alkylene oxide-alkanolamine reaction products can also be, for example, the products of reacting primary, secondary, or tertiary alkanolamines with ethylene, propylene, or higher epoxides in a molar ratio of 1:1 to 1:2. Reactant ratios and temperatures for conducting such reactions are known to those skilled in the art.

[0125] In another embodiment, the hydroxyalkyl-substituted alkylene polyamine can be a compound in which the hydroxyalkyl group is a hydroxy-lower alkyl group, i.e., has fewer than eight carbon atoms. Examples of such hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)ethylenediamine (also known as 2-(2-aminoethylamino)ethanol), N,N-bis(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine, monohydroxypropyl-substituted diethylenetriamine, dihydroxypropyl-substituted tetraethylenepentamine, and N-(3-hydroxybutyl)tetramethylenediamine.

[0126] Arylpolyamines are analogues of the above-mentioned aromatic monoamines. Examples of arylpolyamines include N,N'-di-n-butyl-para-phenylenediamine and bis(para-aminophenyl)methane.

[0127] Heterocyclic mono- and polyamines may include: aziridines, azetidines, azolidines, pyridines, pyrroles, indoles, piperidines, imidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N,N'-diaminoalkylpiperazines, azepines, azocines, azonines, azecines, and tetra-, di-, and perhydro derivatives of any of the foregoing compounds and mixtures of two or more of these heterocyclic amines. Typical heterocyclic amines are saturated 5- and 6-membered heterocyclic amines containing only nitrogen, oxygen, and / or sulfur in the heterocycle, especially piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like. Piperidine, aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substituted piperazines, morpholine, aminoalkyl-substituted morpholines, pyrrolidine and aminoalkyl-substituted pyrrolidines are particularly preferred.Usually, the aminoalkyl substituents are bonded to a nitrogen atom that is part of the heterocycle.

[0128] Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-diaminoethylpiperazine. Hydroxy-heterocyclic polyamines are also suitable; examples include N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine, parahydroxyaniline, and N-hydroxyethylpiperazine.

[0129] Examples of polyalkene-substituted amines are the following: poly(propylene)amine, poly(butene)amine, N,N-dimethylpolyisobutyleneamine; polybutenemorpholine N-,N-poly(butene)ethylenediamine, N-poly(propylene)trimethylenediamine, N-poly(butene), diethylenetriamine, N',N'-poly(butene)tetraethylenepentamine and N,N-dimethyl-N'poly(propylene)-1,3-propylenediamine.

[0130] The number average molecular weight of such polyalkene-substituted amines is about 500 to about 5000, such as 1000 to about 1500 or about 500 to about 3000.

[0131] Any of the above-mentioned polyalkene-substituted amines, which are secondary or primary amines, can be alkylated to tertiary amines with alkylating agents, also known as quaternizing agents, such as dialkyl sulfates, alkyl halides, hydrocarbyl-substituted carbonates; hydrocarbyl epoxides in combination with an acid; and mixtures thereof. When certain quaternizing agents, such as alkyl halides or dialkyl sulfates, are used, it may be necessary to provide a base or basic agents, such as sodium carbonate or sodium hydroxide, to yield the free tertiary amine form. Primary amines require two equivalents of alkylating agent and two equivalents of base to obtain a tertiary amine.In another embodiment, the alkylation of primary amines can often be carried out in four consecutive steps: first, a treatment with the alkylating agent, a second treatment with a base, and then repeating the two steps. In another embodiment, the alkylation of a primary amine is carried out in one step, for example, using two moles of alkyl halide in the presence of an excess of a heterogeneous base, such as sodium carbonate. The polyamine can be exhaustively or partially alkylated in a conventional manner.

[0132] In another embodiment, the alkylation of primary amines and secondary amines to tertiary amines can be carried out with epoxides. Unlike with alkyl halides, when an epoxide is used, no treatment with base is required to obtain the free amine. Typically, when amines are alkylated with epoxides, at least one mole of epoxide is used for each hydrogen atom on the amine. When alkylating to the tertiary amine with an epoxide, neither additional acid nor base is required.

[0133] Furthermore, polyisobutenedimethylamine is particularly preferably obtainable by hydroformylation of polyisobutene (Mn 1000) and subsequent reductive amination with dimethylamine, see Example B of WO 2008 / 060888. A3.4) Reaction products of a hydrocarbyl-substituted acylating agent and a compound containing a nitrogen or oxygen atom and additionally containing at least one quaternizable amino group

[0134] Such compounds are described, for example, in the applicant's WO2013 / 000997, to which reference is hereby expressly made.

[0135] Suitable hydrocarbyl-substituted polycarboxylic acid compounds or hydrocarbyl-substituted acylating agents include: The polycarboxylic acid compounds used are aliphatic di- or polyvalent (e.g. tri- or tetravalent), in particular of di-, tri- or tetracarboxylic acids, and analogues thereof, such as anhydrides or lower alkyl esters (partially or fully esterified), and optionally substituted by one or more (e.g. 2 or 3), in particular a long-chain alkyl radical and / or a high molecular weight hydrocarbyl radical, in particular a polyalkylene radical. Examples are C 3 - C 10 polycarboxylic acids, such as the dicarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and their branched analogues; and the tricarboxylic acid citric acid; and anhydrides or lower alkyl esters thereof.The polycarboxylic acid compounds can also be prepared from the corresponding monounsaturated acids and the addition of at least one long-chain alkyl radical and / or high-molecular-weight hydrocarbyl radical. Examples of suitable monounsaturated acids are fumaric acid, maleic acid, and itaconic acid.

[0136] The hydrophobic "long-chain" or "high-molecular-weight" hydrocarbyl radical, which ensures sufficient solubility of the quaternized product in the fuel, has a number-average molecular weight (M n ) of 85 to 20,000, such as 113 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500. Typical hydrophobic hydrocarbyl radicals are polypropenyl, polybutenyl and polyisobutenyl radicals, e.g. with a number average molecular weight M n of 3,500 to 5,000, 350 to 3,000, 500 to 2,500, 700 to 2,500 and 800 to 1,500.

[0137] Suitable hydrocarbyl substituted compounds are described, for example, in DE 43 19 672 and WO2008 / 138836.

[0138] Suitable hydrocarbyl-substituted polycarboxylic acid compounds also include polymeric, particularly dimeric, forms of such hydrocarbyl-substituted polycarboxylic acid compounds. Dimeric forms contain, for example, two acid anhydride groups, which can be reacted independently of one another with the quaternizable nitrogen compound in the preparation process according to the invention.

[0139] The quaternizable nitrogen compounds reactive with the above polycarboxylic acid compound are selected from a. Hydroxyalkyl-substituted mono- or polyamines having at least one quaternized (e.g. choline) or quaternizable, primary, secondary or tertiary amino group, b. straight-chain or branched, cyclic, heterocyclic, aromatic or non-aromatic polyamines having at least one primary or secondary (anhydride-reactive) amino group and having at least one quaternized or quaternizable, primary, secondary or tertiary amino group; c. piperazines. The quaternizable nitrogen compounds are particularly selected from d. hydroxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines. e.straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; di- or polyamines having at least one primary and at least one quaternary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having one primary and one tertiary amino group; .

[0140] Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those which are provided with at least one, such as 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituted group.

[0141] Examples of "hydroxyalkyl-substituted monoamines" include: N-hydroxyalkyl monoamines, N,N-dihydroxyalkyl monoamines, and N,N,N-trihydroxyalkyl monoamines, where the hydroxyalkyl groups are identical or different and are also defined as above. Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl, or 4-hydroxybutyl.

[0142] Examples of "hydroxyalkyl-substituted polyamines" and especially "hydroxyalkyl-substituted diamines" include (N-hydroxyalkyl)alkylenediamines and N,N-dihydroxyalkylalkylenediamines, where the hydroxyalkyl groups are identical or different and are also defined as above. Hydroxyalkyl represents, in particular, 2-hydroxyethyl, 3-hydroxypropyl, or 4-hydroxybutyl; Alkylene represents, in particular, ethylene, propylene, or butylene.

[0143] Suitable "diamines" are alkylenediamines, as well as their N-alkyl-substituted analogues, such as N-monoalkylated alkylenediamines and N,N- or N,N'-dialkylated alkylenediamines. Alkylene particularly represents straight-chain or branched C 1-7 or C 1-4 alkylene, as defined above. Alkyl particularly represents C 1-4 alkyl as defined above. Examples are in particular ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and isomers thereof, pentanediamine and isomers thereof, hexanediamine and isomers thereof, heptanediamine and isomers thereof, as well as mono- or polyalkylated, such as mono- or di-C 1 -C 4 -alkylated, such as methylated, derivatives of the aforementioned diamine compounds, such as 3-dimethylamino-1-propylamine (DMAPA), N,N-diethylaminopropylamine, and N,N-dimethylaminoethylamine.

[0144] Suitable straight-chain polyamines include, for example, dialkylenetriamine, trialkylenetetramine, tetraalkylenepentamine, pentaalkylenehexamine, and the N-alkyl-substituted analogues thereof, such as N-monoalkylated and N,N- or N,N'-dialkylated alkylenepolyamines. Alkylene represents, in particular, straight-chain or branched C 1-7 or C 1-4 alkylene, as defined above. Alkyl represents, in particular, C 1-4 alkyl as defined above.

[0145] Examples are, in particular, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, pentabutylenehexamine; and the N,N-dialkyl derivatives thereof, in particular the N,N-di-C 1-4 -alkyl derivatives thereof. Examples include: N,N-dimethyldimethylenetriamine, N,N-diethyldimethylenetriamine, N,N-dipropyldimethylenetriamine, N,N-dimethyldiethylene-1,2-triamine, N,N-diethyldiethylene-1,2-triamine, N,N-dipropyldiethylene-1,2-triamine, N,N-dimethyldipropylene-1,3-triamine (ieDMAPAPA) N,N-diethyldipentylene-1,5-triamine, N,N-dipropyldipentylene-1,5-triamine, N,N-dimethyldihexylene-1,6-triamine, N,N-diethyldihexylene-1,6-triamine and N,N-dipropyldihexylene-1,6-triamine,.

[0146] "Aromatic carbocyclic diamines" with two primary amino groups are the diamino-substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthalene, fluorene, indene and phenanthrene.

[0147] "Aromatic or non-aromatic heterocyclic polyamines" with two primary amino groups are the derivatives of the following heterocycles substituted with two amino groups: 5- or 6-membered saturated or monounsaturated heterocycles containing one to two nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members, e.g., tetrahydrofuran, pyrrolidine, isoxazolidine, isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine, pyrroline, piperidine, piperidinyl, 1,3-dioxane, tetrahydropyran, hexahydropyridazine, hexahydropyrimidine, piperazine; 5-membered aromatic heterocycles containing, in addition to carbon atoms, one, two, or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, e.g., furan, thiane, pyrrole, pyrazole, oxazole, thiazole, imidazole, and 1,3,4-triazole; Isoxazole, isothiazole, thiadiazole, oxadiazole 6-membered heterocycles containing, in addition to carbon atoms, one or two or one, two or three nitrogen atoms as ring members, e.g.pyridinyl, pyridazine, pyrimidine, pyrazinyl, 1,2,4-triazine, 1,3,5-triazin-2-yl; .

[0148] "Aromatic or non-aromatic heterocycles having a primary and a tertiary amino group" are, for example, the above-mentioned N-heterocycles which are aminoalkylated on at least one ring N atom and in particular carry an amino-C 1-4 -alkyl group.

[0149] "Aromatic or non-aromatic heterocycles having a tertiary amino group and a hydroxyalkyl group" are, for example, the above-mentioned N-heterocycles which are hydroxyalkylated on at least one ring N atom and in particular carry a hydroxy-C 1-4 alkyl group.

[0150] The following groups of individual classes of quaternizable nitrogen compounds are particularly mentioned: Group 1:

[0151] NAME FORMULA Diamines with primary second N atom Ethylenediamine 1,2-Propylenediamine 1,3-Propylenediamine Isomeric butylenediamines, such as 1,5-pentylenediamine Isomeric pentanediamines, such as Isomeric hexanediamines, such as Isomeric heptanediamines, such as Di- and polyamines with a secondary second N atom Diethylenetriamine (DETA) Dipropylenetriamine (DPTA), 3,3'-Iminobis(N,N-dimethylpropylamine) Triethylenetetramine (TETA) Tetraethylenepentamine (TEPA) Pentaethylenehexamine N-Methyl-3-amino-1-propylamine Bishexamethylenetriamine Aromatics Diaminobenzenes, such as Diaminopyridines, such as Group 2:

[0152] NAME FORMULA Heterocycles 1-(3-Aminopropyl)imidazol 4-(3-Aminopropyl)-morpholine 1-(2-Aminoethylpiperidine) 2-(1-Piperazinyl)ethylamine (AEP) N-Methylpiperazine Amines with a tertiary second N atom 3,3-Diamino-N-methyldipropylamine 3-Dimethylamino-1-propylamine (DMAPA) N,N-Diethylaminopropylamine N,N-Dimethylaminoethylamine Group 3:

[0153] NAME FORMULA Alcohols with primary and secondary amine Ethanolamine 3-Hydroxy-1-propylamine Diethanolamine Diisopropanolamin N-(2-Hydroxyethyl)ethylenediamine Alcohols with tertiary amine Triethanolamine, (2.2 I<,2 II<-nitrilotriethanol) 1-(3-Hydroxypropyl)imidazol Tris(hydroxymethyl)amine 3-Dimethylamino-1-propanol 3-Diethylamino-1-propanol 2-Dimethylamino-1-ethanol 4-Diethylamino-1-butanol

[0154] The reaction of the hydrocarbyl-substituted polycarboxylic acid compound with the quaternizable nitrogen compound can be carried out under thermally controlled conditions, so that essentially no condensation reaction occurs. In particular, no formation of water of reaction is then observed. In particular, such a reaction takes place at a temperature in the range of 10 to 80, in particular 20 to 60 or 30 to 50 °C. The reaction time can be in the range of a few minutes or several hours, for example, about 1 minute up to about 10 hours. The reaction can take place at about 0.1 to 2 atm pressure, but in particular at about atmospheric pressure. For example, an inert gas atmosphere, such as nitrogen, is expedient.

[0155] In particular, the reaction can also be carried out at elevated temperatures that favor condensation, e.g., in the range of 90 to 100 °C or 100 to 170 °C. The reaction time can range from a few minutes to several hours, for example, from about 1 minute to about 10 hours. The reaction can take place at a pressure of about 0.1 to 2 atm, but in particular at approximately atmospheric pressure.

[0156] The reactants are preferably initially introduced in approximately equimolar amounts; if necessary, a slight molar excess of the polycarboxylic acid compound, e.g., 0.05 to 0.5 times, such as 0.1 to 0.3 times, is desirable. If necessary, the reactants can be initially introduced in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are solvents from the Solvesso series, toluene, or xylene. The solvent can also be used, for example, to azeotropically remove condensation water from the reaction mixture. In particular, however, the reactions are carried out without solvent.

[0157] The reaction product thus formed can theoretically be further purified or the solvent removed. However, this is usually not necessary, so the reaction product can be transferred to the next synthesis step, quaternization, without further purification.

[0158] Of particular note is the condensation product of polyisobutylene succinic anhydride (Glissopal ®< SA from BASF, produced from polyisobutene (Mn 1000) and maleic anhydride in a known manner) and N,N-dimethyl-1,3-diaminopropane (CAS 109-55-7), see preparation example 1 of WO 2013 / 000997. A4) Quaternizing agent:

[0159] In a further particular embodiment, the quaternization of the at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent selected from epoxides, in particular hydrocarbyl epoxides. where the R d radicals contained therein are identical or different and represent H or a hydrocarbyl radical, where the hydrocarbyl radical has at least 1 to 10 carbon atoms. In particular, these are aliphatic or aromatic radicals, such as linear or branched C 1-10 alkyl radicals or aromatic radicals, such as phenyl or C 1-4 alkylphenyl.

[0160] Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic alkylene oxides, in particular C 2-12 alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2-pentene oxide; and aromatic-substituted ethylene oxides, such as optionally substituted styrene oxide, in particular styrene oxide or 4-methylstyrene oxide.

[0161] When epoxides are used as quaternizing agents, they are used in the presence of free acids, in particular in the presence of free hydrocarbyl-substituted unsaturated, in particular saturated, optionally substituted, in particular unsubstituted protic acids, such as in particular hydrocarbyl-substituted dicarboxylic acids, in particular hydrocarbyl-substituted C 3 -C 28 or C 3 -C 12 dicarboxylic acids, in particular unsubstituted, saturated C 3 -C 6 dicarboxylic acids.

[0162] Suitable dicarboxylic acids are saturated acids such as malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, undecanedioic acid and dodecanedioic acid or higher molecular weight acids such as terta-, hexa- or octadecanedioic acid substituted acids such as malic acid, α-ketoglutaric acid, oxaloacetic acid; glutamic acid; aspartic acid; and unsaturated acids such as maleic acid and fumaric acid; in particular malonic, succinic, glutaric, adipic and pimelic acid.

[0163] Aromatic dicarboxylic acids such as phthalic acid are also suitable.

[0164] If necessary or desired, hydrocarbyl-substituted dicarboxylic acids can also be used in their anhydride form. For quaternization, the ring opening of the anhydride is then achieved by adding water.

[0165] Further embodiments of hydrocarbyl-substituted dicarboxylic acids: The hydrocarbyl-substituted dicarboxylic acids can be prepared by hydrolysis of the corresponding hydrocarbyl-substituted dicarboxylic anhydrides in a manner known in principle, as described, for example, in DE 2443537. The hydrolysis is preferably carried out with stoichiometric amounts of water at temperatures of 50 to 150°C, but an excess of water can also be used. The hydrolysis can be carried out without a solvent or in the presence of an inert solvent. Typical examples are, for example, solvents from the Solvesso series, toluene, xylene, or straight-chain and branched saturated hydrocarbons such as paraffins or naphthenes. The solvent can be removed after hydrolysis, but preferably it remains and is used as a solvent or co-solvent for the subsequent quaternization.

[0166] Preferred hydrocarbyl-substituted dicarboxylic anhydrides are hydrocarbyl-substituted succinic anhydrides, such as those sold by Pentagon: n-dodecenylsuccinic anhydride CAS 19780-11-1, n-octadecenylsuccinic anhydride CAS 28777-98-2, i-octadecenylsuccinic anhydride CAS 28777-98-2, i-hexadecenylsuccinic anhydride / i-octadecenylsuccinic anhydride CAS 32072-96-1 & 28777-98-2, n-octenylsuccinic anhydride CAS 26680-54-6, and tetrapropenylsuccinic anhydride CAS 26544-38-7.

[0167] Polyisobutenesuccinic anhydride (PIBSA) is also preferred. The production of PIBSA from polyisobutene (PIB) and maleic anhydride (MA) is known in principle and results in a mixture of PIBSA and bismaleic PIBSA (BM PIBSA, see Scheme 1 below), which is generally not purified but processed as such. The ratio of the two components to each other can be expressed as the degree of bismaleic acid (BMG). The BMG is known in principle (see US Pat. No. 5,883,196) and is determined as described in US Pat. No. 5,883,196.

[0168] PIBSA with a degree of bismaleation of up to 30%, preferably up to 25%, and particularly preferably up to 20% is particularly preferred. The degree of bismaleation is generally at least 2%, preferably at least 5%, and particularly preferably at least 10%. Targeted production is described, for example, in US Pat. No. 5,883,196. Highly reactive PIB (HR-PIB) with Mn in the range of 500 to 3000, for example 550 to 2500, 800 to 1200, or 900 to 1100, is particularly suitable for production.

[0169] Mn is determined by GPC as described in US Pat. No. 5,883,196. Particularly preferred PIBSA prepared from HR-PIB (Mn = 1000) has saponification values ​​of 85-95 mg KOH / g.

[0170] A non-limiting example of a particularly suitable PIBSA is Glissopal ®< SA F from BASF, produced from HR-PIB (Mn = 1000) with a bismaleation degree of 15% and a saponification number of 90 mg KOH / g.

[0171] It is also conceivable, although less preferred, to react the above-mentioned hydrocarbyl-substituted dicarboxylic anhydrides with an alcohol, preferably a monoalcohol, particularly preferably an alkanol, or an amine instead of water to form the corresponding monoester or monoamide of the hydrocarbyl-substituted dicarboxylic acids. It is important that an acid function remains in the molecule during such a reaction.

[0172] If the quaternization is carried out in the presence of an alcohol, the same alcohol is preferably used for such a reaction of the hydrocarbyl-substituted dicarboxylic acid anhydrides as the solvent in the quaternization, i.e. preferably 2-ethylhexanol or 2-propylheptanol, as well as butyldiglycol, butylglycol, methoxypropoxypropanol or butoxydipropanol.

[0173] Such an alcoholysis is preferably carried out with stoichiometric amounts of alcohol or amine at temperatures of 50 to 150°C, but an excess of alcohol or amine, preferably alcohol, can also be used. This excess then conveniently remains in the reaction mixture and serves as a solvent in the subsequent quaternization. A5) Production of additives according to the invention: a) Quaternization

[0174] Quaternization with an epoxide of formula (4) is generally carried out following known methods. If the boiling point of a component of the reaction mixture, especially the epoxide, is above the reaction temperature at atmospheric pressure, the reaction is conveniently carried out in an autoclave.

[0175] For example, in an autoclave, a solution of the tertiary amine is mixed with the organic hydrocarbyl-substituted dicarboxylic acid (such as polyisobutenesuccinic acid) in the required approximately stoichiometric amounts. For each equivalent of quaternizable tertiary nitrogen atom, 0.1 to 2.0, 0.2 to 1.5, or 0.5 to 1.25 equivalents of dicarboxylic acid can be used. However, approximately molar proportions of the dicarboxylic acid are preferably used. The reaction mixture is then sufficiently purged with N 2 , a suitable pre-pressure is established, and the epoxide (e.g., propylene oxide) is added in the required stoichiometric amounts at a temperature between 20°C and 180°C. For each equivalent of quaternizable tertiary nitrogen atom, e.g., 0.1 to 4.0, 0.2 to 3, or 0.5 to 2 equivalents of epoxide can be used.In particular, however, approximately 1 to 2 equivalents of epoxide are used relative to the tertiary amine to completely quaternize the tertiary amine group. In particular, a molar excess of alkylene oxide can also be used, whereby the free carboxyl group of the dicarboxylic acid is partially or completely esterified. The reaction mixture is then stirred for a suitable period of time, from a few minutes to about 24 hours, such as about 10 hours at a temperature between 20°C and 180°C (e.g., 50°C), cooled, for example, to about 20 to 50°C, purged with N 2 , and the reactor is emptied.

[0176] The reaction can take place at approximately 0.1 to 20 bar, such as 1 to 10 or 1.5 to 5 bar. However, the reaction can also take place at atmospheric pressure. An inert gas atmosphere, such as nitrogen, is particularly suitable.

[0177] If necessary, the reactants can be pre-dissolved in a suitable inert organic aliphatic or aromatic solvent, or a mixture thereof, for quaternization. Typical examples include solvents from the Solvesso series, toluene or xylene, 2-ethylhexanol, or 2-propylheptanol, as well as butyldiglycol, butylglycol, methoxypropoxypropanol, butoxydipropanol, or straight-chain and branched saturated hydrocarbons such as paraffins or naphthenes. However, quaternization can also be carried out in the absence of a solvent.

[0178] The quaternization can be carried out in the presence of a protic solvent, optionally also in combination with an aliphatic or aromatic solvent. Suitable protic solvents have, in particular, a dielectric constant (at 20°C) of greater than 7. The protic solvent can contain one or more OH groups and can also be water. Suitable solvents can also be alcohols, glycols, and glycol ethers. In particular, suitable protic solvents can be those mentioned in WO 2010132259. Particularly suitable solvents are methanol, ethanol, n-propanol, isopropanol, all isomers of butanol, all isomers of pentanol, all isomers of hexanol, 2-ethylhexanol, 2-propylheptanol, and also mixtures of various alcohols. The presence of a protic solvent can positively influence the conversion and reaction rate of the quaternization. b) Workup of the reaction mixture

[0179] The resulting reaction product can theoretically be further purified or the solvent can be removed. If necessary, excess reagent, such as excess epoxide, can be removed. This can be done, for example, by introducing nitrogen at atmospheric pressure or under reduced pressure. To improve the further processability of the products, solvents can also be added after the reaction, such as solvents from the Solvesso series, 2-ethylhexanol, or essentially aliphatic solvents. However, this is usually not absolutely necessary, so the reaction product can be used as an additive without further purification, optionally after blending with other additive components (see below).

[0180] It is a preferred embodiment of the present invention that the quaternized ammonium compounds have a weight loss in a thermogravimetric analysis (TGA) at 350 °C of less than 50 wt.%, such as less than 40, less than 35, less than 30, less than 20 or less than 15, such as up to 0 to 5 wt.% weight loss.

[0181] For this purpose, a thermogravimetric analysis (TGA) is performed according to ISO 4154. Specifically, the test involves a run from 50°C to 900°C at a temperature ramp rate of 20°C per minute under a nitrogen atmosphere at a flow rate of 60 mL per minute. B) Other additive components

[0182] The fuel additived with the quaternized additive according to the invention is a gasoline fuel or in particular a middle distillate fuel, especially a diesel fuel.

[0183] The fuel may contain other common additives to improve efficiency and / or suppress wear.

[0184] In the case of diesel fuels, these are primarily common detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.

[0185] In the case of gasoline, these are mainly friction modifiers, corrosion inhibitors, demulsifiers, dehazers, antifoam agents, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.

[0186] Typical examples of suitable co-additives are listed in the following section: B1) Detergent additives

[0187] The usual detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical with a number-average molecular weight (M n ) of 85 to 20,000 and at least one polar grouping selected from: (Da) mono- or polyamino groups with up to 6 nitrogen atoms, where at least one nitrogen atom has basic properties; (Db) nitro groups, optionally in combination with hydroxyl groups; (Dc) hydroxyl groups in combination with mono- or polyamino groups, where at least one nitrogen atom has basic properties; (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts; (De) sulfonic acid groups or their alkali metal or alkaline earth metal salts; (Df) polyoxy-C 2 - to C 4 -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, where at least one nitrogen atom has basic properties, or by carbamate groups; (Dg) carboxylic acid ester groups; (Dh) groups derived from succinic anhydride with hydroxyl and / or amino and / or amido and / or imido groups; and / or (Di) moieties produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.

[0188] The hydrophobic hydrocarbon radical in the above detergent additives, which ensures sufficient solubility in the fuel, has a number-average molecular weight (M n ) of 85 to 20,000, preferably of 113 to 10,000, particularly preferably of 300 to 5,000, more preferably of 300 to 3,000, even more preferably of 500 to 2,500 and in particular of 700 to 2,500, especially of 800 to 1,500. As a typical hydrophobic hydrocarbon radical, in particular in combination with the polar, in particular polypropenyl, polybutenyl and polyisobutenyl radicals with a number-average molecular weight M n of preferably in each case 300 to 5,000, particularly preferably 300 to 3,000, more preferably 500 to 2,500, more preferably 700 to 2,500 and especially 800 to 1,500.

[0189] The following may be mentioned as examples of the above groups of detergent additives: Additives containing mono- or polyamino groups (Da) are preferably polyalkene mono- or polyalkene polyamines based on polypropene or on highly reactive (i.e. with predominantly terminal double bonds) or conventional (i.e. with predominantly central double bonds) polybutene or polyisobutene with M n = 300 to 5000, particularly preferably 500 to 2500 and in particular 700 to 2500. Such additives based on highly reactive polyisobutene, which can be prepared from the polyisobutene, which can contain up to 20 wt. % n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known in particular from EP-A 244,616 known.If the additives are produced from polybutene or polyisobutene with predominantly central double bonds (usually in the β- and γ-positions), the production route can be either by chlorination and subsequent amination, or by oxidation of the double bond with air or ozone to form the carbonyl or carboxyl compound, followed by amination under reductive (hydrogenating) conditions. Amines such as ammonia, monoamines, or the aforementioned polyamines can be used for amination. Corresponding polypropene-based additives are described, in particular, in WO-A 94 / 24231.

[0190] Further special additives containing monoamino groups (Da) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97 / 03946.

[0191] Further special additives containing monoamino groups (Da) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.

[0192] Additives containing nitro groups (Db), optionally in combination with hydroxyl groups, are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A96 / 03367 and WO-A 96 / 03479. These reaction products are generally mixtures of pure nitropolyisobutenes (e.g. α,β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g. α-nitro-β-hydroxypolyisobutene). Additives containing hydroxyl groups in combination with mono- or polyamino groups (Dc) are, in particular, reaction products of polyisobutene epoxides, obtainable from polyisobutene with M n = 300 to 5000, preferably containing predominantly terminal double bonds, with ammonia, mono- or polyamines, as described in particular in EP-A 476 485.

[0193] Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of C 2 - to C 40 -olefins with maleic anhydride having a total molecular weight of 500 to 20,000, whose carboxyl groups are fully or partially converted to the alkali metal or alkaline earth metal salts and a remaining residue of the carboxyl groups is converted with alcohols or amines. Such additives are known in particular from EP-A 307 815. Such additives serve primarily to prevent valve seat wear and, as described in WO-A 87 / 01126, can be advantageously used in combination with conventional fuel detergents such as poly(iso)butenamines or polyetheramines.

[0194] Additives containing sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as described in particular in EP-A 639 632. Such additives serve primarily to prevent valve seat wear and can advantageously be used in combination with conventional fuel detergents such as poly(iso)buteneamines or polyetheramines.

[0195] Additives containing polyoxy-C 2 -C 4 -alkylene groups (Df) are preferably polyethers or polyetheramines, which are obtainable by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4 877 416. In the case of polyethers, such products also fulfill carrier oil properties. Typical examples are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates, and polyisobutenol butoxylates and propoxylates, as well as the corresponding reaction products with ammonia.

[0196] Additives containing carboxylic acid ester groups (Dg) are preferably esters of mono-, di-, or tricarboxylic acids with long-chain alkanols or polyols, especially those with a minimum viscosity of 2 mm² / s at 100°C, as described in particular in DE-A 38 38 918. Aliphatic or aromatic acids can be used as mono-, di-, or tricarboxylic acids; long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols. Typical representatives of esters are adipates, phthalates, isophthalates, terephthalates, and trimellitates of isooctanol, isononanol, isodecanol, and isotridecanol. Such products also fulfill carrier oil properties.

[0197] Additives derived from succinic anhydride containing moieties containing hydroxyl and / or amino and / or amido and / or in particular imido groups (Dh) are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenylsuccinic anhydride, which are obtainable by reacting conventional or highly reactive polyisobutene with M n = preferably 300 to 5000, particularly preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and in particular 800 to 1500, with maleic anhydride by thermal means in an ene reaction or via the chlorinated polyisobutene.The groups with hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, also have free amine groups, succinic acid derivatives with one acid and one amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, also have free amine groups, or diimides formed by the reaction of di- or polyamines with two succinic acid derivatives. However, in the presence of imido groups D(h), the further detergent additive within the meaning of the present invention is only used up to a maximum of 100% of the amount by weight of compounds with a betaine structure. Such fuel additives are generally known and described, for example, in documents (1) and (2).These are preferably the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines, and particularly preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest here are reaction products with aliphatic polyamines (polyalkyleneimines), such as, in particular, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine, which have an imide structure.

[0198] Additives containing (Di) groups produced by the Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or dimethylaminopropylamine. The polyisobutenyl-substituted phenols can originate from conventional or highly reactive polyisobutene with M n = 300 to 5000. Such "polyisobutene Mannich bases" are described in particular in EP-A 831 141.

[0199] One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosage rate of these detergent additives is preferably 25 to 2500 ppm by weight, in particular 75 to 1500 ppm by weight, especially 150 to 1000 ppm by weight. B2) Carrier oils

[0200] Carrier oils used can be mineral or synthetic. Suitable mineral carrier oils include fractions obtained during petroleum processing, such as brightstock or base oils with viscosities such as SN 500 to 2000, as well as aromatic hydrocarbons, paraffinic hydrocarbons, and alkoxyalkanols. Also suitable is a fraction known as "hydrocrack oil" obtained during mineral oil refining (a vacuum distillate cut with a boiling range of approximately 360 to 500 °C, obtained from natural mineral oil catalytically hydrogenated, isomerized, and dewaxed under high pressure). Blends of the above-mentioned mineral carrier oils are also suitable.

[0201] Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternal olefins), (poly)esters, poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols.

[0202] Examples of suitable polyolefins are olefin polymers with M n = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

[0203] Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C2- to C4-alkylene groups, which are obtainable by reacting C2- to C60-alkanols, C6- to C30-alkanediols, mono- or di-C2- to C30-alkylamines, C1- to C30-alkylcyclohexanols or C1- to C30-alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, poly-C 2 - to C 6 -alkylene oxide amines or functional derivatives thereof can be used as polyetheramines.Typical examples are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates as well as polyisobutenol butoxylates and propoxylates as well as the corresponding reaction products with ammonia.

[0204] Examples of carboxylic acid esters of long-chain alkanols include, in particular, esters of mono-, di-, or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918. Aliphatic or aromatic acids can be used as mono-, di-, or tricarboxylic acids; long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols. Typical examples of esters are adipates, phthalates, isophthalates, terephthalates, and trimellitates of isooctanol, isononanol, isodecanol, and isotridecanol, e.g., di-(n- or isotridecyl)phthalate.

[0205] Other suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.

[0206] Examples of particularly suitable synthetic carrier oils are alcohol-initiated polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30, and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, e.g., propylene oxide, n-butylene oxide, and isobutylene oxide units, or mixtures thereof, per alcohol molecule. Non-limiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is, in particular, a straight-chain or branched C 6 - to C 18 -alkyl radical. Particular examples include tridecanol and nonylphenol. Particularly preferred alcohol-initiated polyethers are the reaction products (polyetherification products) of monohydric aliphatic C 6 - to C 18 -alcohols with C 3 - to C 6 -alkylene oxides.Examples of monohydric aliphatic C6-C18 alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, and their constitutional and positional isomers. The alcohols can be used both in the form of the pure isomers and in the form of technical mixtures. A particularly preferred alcohol is tridecanol. Examples of C3- to C6-alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, or tetrahydrofuran, pentylene oxide, and hexylene oxide. Particularly preferred among these are C 3 - to C 4 -alkylene oxides, ie, propylene oxide such as 1,2-propylene oxide, and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide, and isobutylene oxide. Butylene oxide is used specifically.

[0207] Other suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.

[0208] Special carrier oils are synthetic carrier oils, with the alcohol-started polyethers described above being particularly preferred.

[0209] The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 1 to 1000 ppm by weight, particularly preferably 10 to 500 ppm by weight and in particular 20 to 100 ppm by weight. B3) Cold flow improvers

[0210] Suitable cold flow improvers are, in principle, any organic compound capable of improving the flow behavior of middle distillate fuels or diesel fuels in cold conditions. For this purpose, they must exhibit sufficient oil solubility. In particular, the cold flow improvers ("middle distillate flow improvers" or "MDFIs") commonly used in middle distillates of fossil origin, i.e., in conventional mineral diesel fuels, are suitable for this purpose. However, organic compounds can also be used that, when used in conventional diesel fuels, partially or predominantly exhibit the properties of a wax anti-settling additive ("WASA"). They can also partially or predominantly act as nucleators. However, mixtures of organic compounds effective as MDFIs and / or WASAs and / or nucleators can also be used.

[0211] Typically, the cold flow improver is selected from: (K1) copolymers of a C 2 - to C 40 -olefin with at least one further ethylenically unsaturated monomer; (K2) comb polymers; (K3) polyoxyalkylenes; (K4) polar nitrogen compounds; (K5) sulfocarboxylic acids or sulfonic acids or derivatives thereof; and (K6) poly(meth)acrylic acid esters.

[0212] Mixtures of different representatives from one of the respective classes (K1) to (K6) as well as mixtures of representatives from different classes (K1) to (K6) can be used.

[0213] Suitable C 2 - to C 40 -olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10, carbon atoms, and having 1 to 3, preferably 1 or 2, in particular one carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged either terminally (α-olefins) or internally. However, α-olefins are preferred, particularly preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene, and especially ethylene.

[0214] In the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic acid alkenyl esters, (meth)acrylic acid esters and other olefins.

[0215] If additional olefins are polymerized, they are preferably higher molecular weight than the above-mentioned C 2 - to C 40 -olefin base monomers. For example, if ethylene or propene is used as the olefin base monomer, C 10 - to C 40 -α-olefins are particularly suitable as additional olefins. In most cases, additional olefins are only polymerized if monomers with carboxylic acid ester functions are also used.

[0216] Suitable (meth)acrylic acid esters are, for example, esters of (meth)acrylic acid with C 1 to C 20 alkanols, in particular C 1 to C 10 alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol as well as structural isomers thereof.

[0217] Suitable carboxylic acid alkenyl esters are, for example, C 2 - to C 14 -alkenyl esters, e.g., the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Vinyl esters are preferred. Among the carboxylic acids with a branched hydrocarbon radical, those whose branching is located in the α-position to the carboxyl group are preferred, with the α-carbon atom particularly preferably being tertiary, i.e., the carboxylic acid is a so-called neocarboxylic acid. However, the hydrocarbon radical of the carboxylic acid is preferably linear.

[0218] Examples of suitable alkenyl carboxylic acid esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate, and the corresponding propenyl esters, with vinyl esters being preferred. A particularly preferred alkenyl carboxylic acid ester is vinyl acetate; typical resulting copolymers of group (K1) are the most frequently used ethylene-vinyl acetate copolymers ("EVA"). Particularly advantageously usable ethylene-vinyl acetate copolymers and their preparation are described in WO 99 / 29748.

[0219] Also suitable as copolymers of class (K1) are those containing two or more different alkenyl carboxylic acid esters in copolymerized form, which differ in the alkenyl function and / or the carboxylic acid group. Copolymers containing, in addition to the alkenyl carboxylic acid ester(s), at least one olefin and / or at least one (meth)acrylic acid ester in copolymerized form are also suitable.

[0220] Terpolymers of a C 2 - to C 40 -α-olefin, a C 1 - to C 20 -alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms, and a C 2 - to C 14 -alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also suitable as copolymers of class (K1). Such terpolymers are described in WO 2005 / 054314. A typical terpolymer of this type is composed of ethylene, 2-ethylhexyl acrylate, and vinyl acetate.

[0221] The at least one or more ethylenically unsaturated monomers are copolymerized into the copolymers of class (K1) in an amount of preferably 1 to 50 wt.%, in particular 10 to 45 wt.%, and especially 20 to 40 wt.%, based on the total copolymer. The majority by weight of the monomer units in the copolymers of class (K1) thus generally originates from the C 2 to C 40 base olefins.

[0222] The copolymers of class (K1) preferably have a number-average molecular weight M n of 1000 to 20,000, particularly preferably of 1000 to 10,000 and in particular of 1000 to 8000.

[0223] Typical comb polymers of component (K2) are obtainable, for example, by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example, with an α-olefin or an unsaturated ester such as vinyl acetate, followed by esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms. Other suitable comb polymers are copolymers of α-olefins and esterified comonomers, for example, esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers can also be polyfumarates or polymaleates. Homo- and copolymers of vinyl ethers are also suitable comb polymers. Comb polymers suitable as components of class (K2) include, for example, those described in WO 2004 / 035715 and in "Comb-Like Polymers. Structure and Properties," NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs.8, pages 117 to 253 (1974). Mixtures of comb polymers are also suitable.

[0224] Polyoxyalkylenes suitable as components of class (K3) include, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester-ethers, and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two, linear alkyl groups, each having 10 to 30 carbon atoms, and one polyoxyalkylene group with a number-average molecular weight of up to 5000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US Pat. No. 4,491,455. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols with a number-average molecular weight of 100 to 5000. Polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid, are also suitable.

[0225] Polar nitrogen compounds suitable as components of class (K4) can be both ionic and non-ionic in nature and preferably have at least one, in particular at least two substituents in the form of a tertiary nitrogen atom of the general formula >NR 7<, wherein R 7< represents a C 8 - to C 40 -hydrocarbon radical. The nitrogen substituents can also be quaternized, i.e. in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides, which are obtainable by reacting at least one amine substituted by at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably contain at least one linear C 8 - to C 40 -alkyl radical.Suitable primary amines for the preparation of the polar nitrogen compounds mentioned include octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, and the higher linear homologues. Suitable secondary amines include dioctadecylamine and methylbehenylamine. Amine mixtures are also suitable for this purpose, particularly industrially accessible amine mixtures such as fatty amines or hydrogenated tall amines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, Aliphatic." Acids suitable for the reaction include cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and succinic acids substituted with long-chain hydrocarbon radicals.

[0226] In particular, the component of class (K4) is an oil-soluble reaction product of poly(C 2 - to C 20 -carboxylic acids) containing at least one tertiary amino group with primary or secondary amines. The poly(C 2 - to C 20 -carboxylic acids) containing at least one tertiary amino group on which this reaction product is based preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units. The carboxylic acid units are linked in a suitable manner to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. They are preferably bonded to tertiary nitrogen atoms, which, in the case of multiple nitrogen atoms, are linked via hydrocarbon chains.

[0227] Preferably, the component of class (K4) is an oil-soluble reaction product based on poly(C 2 - to C 20 -carboxylic acids) of the general formula IIa or IIb containing at least one tertiary amino group

[0228] in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III and the variable B denotes a C 1 to C 19 alkylene group. The compounds of general formula IIa and IIb exhibit, in particular, the properties of a WASA.

[0229] Furthermore, the preferred oil-soluble reaction product of component (K4), in particular that of the general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.

[0230] Examples of straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene), and especially 1,2-ethylene. The variable A preferably comprises 2 to 4, in particular 2 or 3, carbon atoms.

[0231] C1 to C19 alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene, and especially methylene. The variable B preferably comprises 1 to 10, in particular 1 to 4, carbon atoms.

[0232] The primary and secondary amines used as reaction partners for the polycarboxylic acids to form component (K4) are typically monoamines, especially aliphatic monoamines. These primary and secondary amines can be selected from a variety of amines bearing hydrocarbon radicals, optionally linked to one another.

[0233] These amines underlying the oil-soluble reaction products of component (K4) are usually secondary amines and have the general formula HN(R 8< ) 2 , in which the two variables R 8< independently of one another each represent straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C 24 -alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the said secondary amines are derived, with regard to their longer-chain alkyl radicals, from naturally occurring fatty acids or their derivatives. The two radicals R 8< are preferably identical.

[0234] The secondary amines mentioned can be bonded to the polycarboxylic acids via amide structures or in the form of ammonium salts; it is also possible for only a portion to be present as amide structures and another portion as ammonium salts. Preferably, only a few or no free acid groups are present. The oil-soluble reaction products of component (K4) are preferably present entirely in the form of amide structures.

[0235] Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid, or propylene-1,2-diaminetetraacetic acid, each containing 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, dipalmitinamine, dicoconut fatty amine, distearylamine, dibehenylamine, or, in particular, ditallow fatty amine. A particularly preferred component (K4) is the reaction product of 1 mol of ethylenediaminetetraacetic acid and 4 mol of hydrogenated ditallow fatty amine.

[0236] Further typical examples of component (K4) are the N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates, for example the reaction product of 1 mol of phthalic anhydride and 2 mol of ditallow fatty amine, the latter being hydrogenated or non-hydrogenated, and the reaction product of 1 mol of an alkenylspirobislactone with 2 mol of a dialkylamine, for example ditallow fatty amine and / or tallow fatty amine, the latter two being hydrogenated or non-hydrogenated.

[0237] Other typical structural types for the component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93 / 18115.

[0238] Sulfocarboxylic acids, sulfonic acids or their derivatives suitable as cold flow improvers of the component of class (K5) are, for example, the oil-soluble carboxylic acid amides and carboxylic acid esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957.

[0239] Poly(meth)acrylic acid esters suitable as cold flow improvers for the component of class (K6) include both homopolymers and copolymers of acrylic and methacrylic acid esters. Copolymers of at least two different (meth)acrylic acid esters that differ in the condensed alcohol are preferred. Optionally, the copolymer also contains a further, different, olefinically unsaturated monomer as copolymerized units. The weight-average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C14 and C15 alcohols, the acid groups being neutralized with hydrogenated tallamine. Suitable poly(meth)acrylic acid esters are described, for example, in WO 00 / 44857.

[0240] The cold flow improver or the mixture of various cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, particularly preferably 20 to 2000 ppm by weight, more preferably 50 to 1000 ppm by weight and in particular 100 to 700 ppm by weight, e.g. 200 to 500 ppm by weight. B4) Lubricity improvers

[0241] Suitable lubricity improvers (or friction modifiers) are typically based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described, for example, in WO 98 / 004656, and glycerol monooleate. The reaction products of natural or synthetic oils, such as triglycerides, and alkanolamines described in US Pat. No. 6,743,266 B2 are also suitable as such lubricity improvers. B5) Corrosion inhibitors

[0242] Suitable corrosion inhibitors include succinic acid esters, especially with polyols, fatty acid derivatives, e.g. oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products marketed under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Afton Corporation). B6) Demulsifiers

[0243] Suitable demulsifiers are, for example, the alkali or alkaline earth metal salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth metal salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes. B7) Dehazer

[0244] Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, such as the products available under the trade name NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite). B8) Antifoam agents

[0245] Suitable antifoam agents are, for example, polyether-modified polysiloxanes, such as the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc). B9) Cetane number improvers

[0246] Suitable cetane number improvers include aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate as well as peroxides such as di-tert-butyl peroxide. B10) Antioxidants

[0247] Suitable antioxidants include substituted phenols such as 2,6-di-tert.-butylphenol and 6-di-tert.-butyl-3-methylphenol as well as phenylenediamines such as N,N'-di-sec.-butyl-p-phenylenediamine. B11) Metal deactivators

[0248] Suitable metal deactivators include salicylic acid derivatives such as N,N'-disalicylidene-1,2-propanediamine. B12) Solvent

[0249] Suitable solvents include nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, such as toluene, xylenes, white spirit, and products sold under the trade names SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents, such as alcohols such as 2-ethylhexanol, decanol, and isotridecanol. Such solvents usually enter diesel fuel together with the aforementioned additives and co-additives intended to dissolve or dilute them for improved handling. B13) Auxiliary substances against deposits in injectors

[0250] A further preferred embodiment is to combine the compounds according to the invention with further auxiliaries against internal and external deposits in injectors in diesel engines.

[0251] These can preferably be olefin-polymerizable carboxylic acid copolymers, wherein the copolymer contains at least one free carboxylic acid side group, or a nitrogen compound quaternized with epoxide in the presence of an olefin-polymerizable carboxylic acid copolymer, wherein the copolymer contains at least one free carboxylic acid side group, wherein the polymerizable carboxylic acid is a polymerizable mono- or polycarboxylic acid.

[0252] Furthermore, they may be copolymers, copolymer-containing reaction products, or a copolymer-containing partial fraction thereof, wherein the copolymer is obtainable by (1) Copolymerization of a) at least one ethylenically unsaturated, polymerizable polycarboxylic acid anhydride with b) at least one polymerizable olefin; (2) subsequent derivatization of the copolymer from step (1) by partial or complete reaction of the anhydride residues of the copolymer from step (1) with water, at least one hydroxyl compound, at least one primary or secondary amine; or mixtures thereof, to form a carboxyl-containing copolymer derivative; and optionally (3) quaternization of a quaternizable (in particular tertiary) nitrogen compound with an epoxide and the copolymer derivative from step (2).

[0253] Furthermore, they may be copolymers, copolymer-containing reaction products, or a copolymer-containing partial fraction thereof, wherein the copolymer is obtainable by (1) Copolymerization of a) at least one ethylenically unsaturated, polymerizable mono- or polycarboxylic acid with b) at least one polymerizable olefin; (2) subsequent derivatization of the copolymer from step (1) by partial reaction of the carboxyl radicals of the copolymer with at least one hydroxyl compound, at least one primary or secondary amine; or mixtures thereof, to form a copolymer derivative having a reduced content of free carboxyl groups; and optionally (3) quaternization of a quaternizable nitrogen compound with an epoxide and the copolymer derivative from step (2).

[0254] Furthermore, they may be copolymers, copolymer-containing reaction products, or a copolymer-containing partial fraction thereof, wherein the copolymer is obtainable by (1) copolymerization of a) at least one ethylenically unsaturated, polymerizable mono- or polycarboxylic acid with b) at least one polymerizable olefin and optionally (2) quaternization of a quaternizable nitrogen compound with an epoxide and the hydrolysis product from step (1);

[0255] Such copolymer compounds are described, for example, in the present applicant's European patent application EP application number 14152991.7. C) Fuels

[0256] The additive according to the invention is outstandingly suitable as a fuel additive and can, in principle, be used in any fuel. It produces a whole range of advantageous effects when operating internal combustion engines with fuels. The quaternized additive according to the invention is preferably used in middle distillate fuels, especially diesel fuels.

[0257] The present invention therefore also provides fuels, in particular middle distillate fuels, with an effective content of the quaternized additive according to the invention as an additive for achieving advantageous effects during the operation of internal combustion engines, for example diesel engines, in particular direct-injection diesel engines, especially diesel engines with common-rail injection systems. This effective content (dosage rate) is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, in each case based on the total amount of fuel.

[0258] Middle distillate fuels such as diesel fuels or heating oils are preferably petroleum raffinates, which typically have a boiling range of 100 to 400°C. These are usually distillates with a 95% boiling point of up to 360°C or even higher. However, they can also be so-called "ultra-low sulfur diesel" or "city diesel," characterized by a 95% boiling point of, for example, a maximum of 345°C and a sulfur content of a maximum of 0.005 wt.%, or by a 95% boiling point of, for example, 285°C and a sulfur content of a maximum of 0.001 wt.%. In addition to the mineral middle distillate fuels or diesel fuels obtainable through refining, those obtainable through coal gasification or gas liquefaction [gas to liquid (GTL) fuels] or biomass liquefaction [biomass to liquid (BTL) fuels] are also suitable. Mixtures of the middle distillate fuels mentioned above are also suitable.Diesel fuels with renewable fuels such as biodiesel or bioethanol. Hydrogenated vegetable oils (HVO) or used kitchen oil (UKO) are also conceivable.

[0259] The qualities of heating oils and diesel fuels are specified in more detail in DIN 51603 and EN 590, for example (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A12, p. 617 ff.).

[0260] In addition to its use in the above-mentioned middle distillate fuels of fossil, vegetable, or animal origin, which are essentially hydrocarbon mixtures, the quaternized additive according to the invention can also be used in mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are also encompassed by the term "middle distillate fuel" within the meaning of the present invention. They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt.%, in particular 3 to 10 wt.%, based on the total amount of middle distillate of fossil, vegetable, or animal origin and biofuel oil.

[0261] Biofuel oils are generally based on fatty acid esters, preferably essentially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats. Alkyl esters are typically understood to be lower alkyl esters, in particular C1 to C4 alkyl esters, which are obtainable by transesterification of the glycerides, especially triglycerides, found in vegetable and / or animal oils and / or fats using lower alcohols, for example, ethanol or especially methanol ("FAME"). Typical lower alkyl esters based on vegetable and / or animal oils and / or fats that are used as biofuel oil or components therefor include sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME"), and especially rapeseed oil methyl ester ("RME"). Hydrogenated vegetable oils (HVO) or used kitchen oil (UKO) are also conceivable.

[0262] The middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, that is to say with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001% by weight of sulfur.

[0263] All commercially available gasoline compositions are suitable. A typical example is the commercially available Eurosuper base fuel according to EN 228. Furthermore, gasoline compositions specified in WO 00 / 47698 are also possible applications for the present invention.

[0264] The quaternized additive according to the invention is particularly suitable as a fuel additive in fuel compositions, in particular in diesel fuels, to overcome the problems described above in direct-injection diesel engines, especially in those with common-rail injection systems.

[0265] Preferred additives in such fuels are the specific compound classes (A) and (C) listed below: Preferred additives (A) are compounds derived from succinic anhydride with long-chain hydrocarbon radicals generally containing 15 to 700, especially 30 to 200, carbon atoms. These compounds may contain further functional groups, preferably selected from hydroxyl, amino, amido, and / or imido groups. Preferred additives are the corresponding derivatives of polyalkenylsuccinic anhydride, which are obtainable, for example, by reacting polyalkenes with maleic anhydride thermally or via the chlorinated hydrocarbons. The number-average molecular weight of the long-chain hydrocarbon radicals is preferably in a range from about 200 to 10,000, particularly preferably 400 to 5,000, in particular 600 to 3,000, and especially 650 to 2,000.These long-chain hydrocarbon radicals are preferably derived from conventional, and in particular from the aforementioned reactive polyisobutenes. Of particular interest as additives (A) are the derivatives of polyalkenylsuccinic anhydrides with ammonia, monoamines, polyamines, monoalcohols, and polyols. Polyamines preferred for derivatization include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, etc. Suitable alcohols include monohydric alcohols such as ethanol, allyl alcohol, dodecanol, and benzyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,2-butanediol, neopentyl glycol, glycerol, trimethylolpropane, erythritol, pentaerythritol, mannitol, and sorbitol.

[0266] Succinic anhydride derivatives (A) suitable as additives are described, for example, in US 3,522,179, US 4,234,435, US 4,849,572, US 4,904,401, US 5,569,644 and US 6,165,235, which are hereby incorporated by reference in their entirety.

[0267] Preferred additives (C) are Mannich adducts. Such adducts are obtained in principle by the Mannich reaction of aromatic hydroxyl compounds, especially phenol and phenol derivatives, with aldehydes and mono- or polyamines. They are preferably the reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, etc. Suitable Mannich adducts and processes for their preparation are described, for example, in US Pat. No. 5,876,468, EP-A 831,141, EP-A 1,233,990, and EP-A 1,226,188, which are hereby incorporated by reference.

[0268] The additives (A) and (C) and optionally further additives mentioned above can usually be used in amounts of 0.0001 to 1 wt.%, preferably 0.001 to 0.6 wt.% and in particular 0.0015 to 0.4 wt.%, based on the total amount of the fuel composition.

[0269] The invention will now be described in more detail with reference to the following exemplary embodiments. In particular, the test methods mentioned below are part of the general disclosure of the application and are not limited to the specific exemplary embodiments. Experimental part: A. General test methods Engine test 1. XUD9 Test - Determination of Flow Restriction

[0270] The implementation is carried out according to the standard provisions of CEC F-23-1-01. 2. DW10 Test - Determination of power loss due to injector deposits in common rail diesel engines 2.1. DW10-KC - Keep Clean Test

[0271] The Keep Clean test is based on the CEC test procedure F-098-08 Issue 5. The same test setup and engine type (PEUGEOT DW10) are used as in the CEC procedure. Changes and special features:

[0272] Cleaned injectors were used in the tests. The cleaning time in an ultrasonic bath containing 60°C water + 10% Superdecontamine (Intersciences, Brussels) was 4 hours. Test run times:

[0273] Unless otherwise stated, the test period was 12 hours without shutdown phases. Figure 1 The one-hour test cycle shown in CEC F-098-08 was run through 12 times. Performance determination (unless otherwise stated):

[0274] The initial power P0,KC [kW] is calculated from the measured torque at 4000 rpm full load immediately after the test start and engine warm-up. The procedure is described in Issue 5 of the test procedure (CEC F-98-08). The same test setup and the PEUGEOT DW10 engine type are used.

[0275] The final power (Pend,KC) is determined in the 12th cycle in stage 12 (see table, Figure 2 ). Here, too, the operating point is 4000 rpm at full load. Pend,KC [kW] is calculated from the measured torque.

[0276] The power loss in the KC test is calculated as follows: Powerloss , KC % = 1 − Pend , KC P 0 , KC ∗ 100 2.2. DW10-Dirty Up - Clean Up-(DU-CU)

[0277] The DU-CU test is based on the CEC Test Procedure F-098-08 Issue 5. The procedure is described in Issue 5 of the test procedure (CEC F-98-08). The same test setup and the PEUGEOT DW10 engine type are used.

[0278] The DU - CU test consists of two separate tests that are run consecutively. The first test is used to determine deposit formation (DU), the second to remove the deposits (CU). After the DU test, the power loss is determined. After the DU test, the engine is not operated for at least 8 hours and allowed to cool to ambient temperature. The CU is then started with CU fuel without removing and cleaning the injectors. Ideally, the deposits and power loss will decrease during the CU test. Changes and special features:

[0279] Cleaned injectors were installed in the engine before each DU test. Cleaning time in an ultrasonic bath at 60°C water + 10% Superdecontamine (Intersciences, Brussels) was 4 hours. Test run times (unless otherwise stated):

[0280] The test period was 4.28 hours for the DU and 8 hours or 12 hours for the CU. The engine was operated without shutdown phases in the DU and CU tests.

[0281] The Figure 1 The one-hour test cycle shown in CEC F-098-08 was run through 12 times each.

[0282] In some DU tests, an accelerated procedure was applied. Instead of using the test cycle from CEC F-098-08, the engine was operated at 4000 rpm full load with an increased amount of Zn (3 ppm instead of 1 ppm in the CEC F-098-08 procedure). Performance determination:

[0283] The initial power P0,du [kW] is calculated from the measured torque at 4000 rpm full load immediately after the test start and engine warm-up. The procedure is also described in Issue 5 of the test procedure.

[0284] The final power (Pend,du) is determined in the 12th cycle at stage 12 (see table above). Here, too, the operating point is 4000 rpm at full load. Pend,du [kW] is calculated from the measured torque.

[0285] The power loss in the DU is calculated as follows Powerloss , du % = 1 − Pend , du P 0 , du ∗ 100 Clean-up

[0286] The initial power P0,cu [kW] is calculated from the measured torque at 4000 rpm full load immediately after the test start and engine warm-up in the CU. The procedure is also described in Issue 5 of the test procedure.

[0287] The final power (Pend,cu) is determined in the 12th cycle in stage 12 (see table Figure 2 ). Here, too, the operating point is 4000 rpm at full load. Pend,cu [kW] is calculated from the measured torque.

[0288] The power loss in the CU test is calculated as follows (a negative number in the power loss in the CU test means an increase in power) Powerloss DU CU % = Pend , du − pend , cu P 0 , du ∗ 100

[0289] A commercially available diesel fuel from Haltermann (RF-06-03) was used as the fuel. 1 ppm by weight of zinc in the form of a zinc didodecanoate solution was added to artificially stimulate the formation of deposits on the injectors. 3. IDID test - Determination of additive effect against internal injector deposits

[0290] The formation of deposits inside the injector was characterized by the deviations of the exhaust gas temperatures of the cylinders at the cylinder outlet during cold start of the DW10 engine.

[0291] To promote deposit formation, 1 mg / l Na in the form of a salt of an organic acid (sodium naphthenate), 20 mg / l dodecenylsuccinic acid and 10 mg / l water were added to the fuel.

[0292] The test is performed as a dirty-up-clean-up test (DU-CU).

[0293] DU-CU is based on the CEC test procedure F-098-08 Issue 5.

[0294] The DU - CU test consists of two separate tests that are run consecutively. The first test is used to determine deposit formation (DU), the second to remove deposits (CU).

[0295] After the DU run, after a standstill phase of at least eight hours, a cold start of the engine is carried out followed by 10 minutes of idle time.

[0296] The CU is then started with the CU fuel without removing and cleaning the injectors. After the CU run for 8 hours, a cold start of the engine is performed after a minimum eight-hour standstill phase, followed by a 10-minute idle. The evaluation is performed by comparing the temperature curves for the individual cylinders after the cold start of the CU and the CU run.

[0297] The IDID test indicates the formation of internal deposits in the injector. The exhaust gas temperature of the individual cylinders serves as the parameter for this test. In an injector system without IDID, the exhaust gas temperatures of the cylinders increase evenly. With IDID present, the exhaust gas temperatures of the individual cylinders do not increase evenly and differ from each other.

[0298] The temperature sensors are located behind the cylinder head outlet in the exhaust manifold. Significant deviations in individual cylinder temperatures (e.g., > 20°C) indicate the presence of internal injector deposits (IDID).

[0299] The tests (DU and CU) are conducted with a running time of 8 hours each. The one-hour test cycle from CEC F-098-08 (see Figure 3) is run 8 times each. If the individual cylinder temperatures deviate from the average of all four cylinders by more than 45°C, the test is aborted prematurely.

[0300] Changes and special features: Cleaned injectors were installed before each DU test. The cleaning time in an ultrasonic bath at 60°C water + 10% Superdecontamine was 4 hours.

[0301] B. Manufacturing examples:

[0302] Production examples 1 to 4: Quaternization of tertiary fatty amines with propylene oxide in the presence of various hydrocarbyl-substituted succinic acids R 1 represents long-chain hydrocarbyl; R 2 , R 3 and R 4 correspond to R a , R b and R c are as defined above; R 5 corresponds to R d as defined above; and R represents H or is a radical generated by esterification with the epoxide, such as -CH 2 CH(R 5 )OH a) Reagents used: Polyisobutylene succinic anhydride (PIBSA, Glissopal ®< SA, BASF):

[0303] Produced from maleic anhydride and polyisobutene 1000 in a known manner. Unless otherwise stated, grades with a degree of bismaleination of 10 to 20% and saponification numbers in the range of 84-95 mg KOH / g were used for the preparation examples according to the invention. To produce polyisobutylenesuccinic acid, polyisobutylenesuccinic anhydride was mixed with an equimolar amount of water corresponding to the saponification number and hydrolyzed at a temperature of 80°C. For example, the reaction of polyisobutylenesuccinic anhydride (saponification number 85.6 mg KOH / g) yielded a reaction product with an acid number of 83.9 mg KOH / g after a reaction time of 4 hours at 80°C. The formation of polyisobutylenesuccinic acid was confirmed by IR spectroscopy (1711 cm -1 < ).

[0304] In an analogous manner, tetrapropenylsuccinic anhydride (CAS 26544-38-7) and a mixed i-hexadecenyl / i-octadecenylsuccinic anhydride (CAS 32072-96-1 and 28777-98-2) from Pentagon were hydrolyzed to the corresponding succinic acid derivatives.

[0305] Cocoyldimethylamine: (N,N-Dimethyl-N-C12 / 14-amine, CAS 68439-70-3 or 112-18-5) with a total amine value of 246 mg KOH / g.

[0306] N-Methyl-N,N-Ditallow fatty amine: Armeen ®< M2HT from Akzo Nobel, CAS 61788-63-4, with a total amine value of 108 mg KOH / g.

[0307] Also used were N,N-dimethylhexadecylamine (nC 16 H 33 NMe 2 , CAS 112-69-6, Aldrich) and tridecylamine (branched; mixture of isomers, CAS 86089-17-0) from BASF.

[0308] N,N-Dimethyl-1,3-diaminopropane (DMAPA, CAS 109-55-7) from BASF.

[0309] 2-Ethylhexanol and 2-Propylheptanol from BASF.

[0310] Solvent Naphtha naphthalene depleted (ND): Solvesso ™< 150 ND der Fa. Exxon Mobil. b) General synthesis procedure

[0311] A solution of the tertiary amine (1 eq. corresponding to the total amine number) and the alkylene succinic acid derivative (1 eq. corresponding to the acid number) in the specified solvent (2-ethylhexanol, unless otherwise stated) is placed in a 2 l autoclave. The amount of solvent and the batch size are selected so that the final product has an active content of 50% and the reactor is filled to approximately 70%. The mixture is then purged three times with N 2 , an inlet pressure of approximately 2 bar N 2 is set, and the temperature is increased to 50°C. The specified alkylene oxide, or propylene oxide (2 eq.) unless otherwise stated, is added over the course of 1 h. The mixture is then stirred for a further 15 h at 50°C, cooled to 25°C, purged with N 2 , and the reactor is emptied. The product is transferred to a 2 l jacketed reactor and excess alkylene oxide is removed by introducing a N 2 stream (10 l / h) under vacuum (70 mbar) at 50°C for 6 h.1< H-NMR (CDCl 3 ) confirms quaternization (δ = 3.3 ppm, singlet, R 2 N(CH 3 ) 2 or R 3 NCH 3 ). c) Tests carried out

[0312] Following the above synthesis procedure, the following quaternizations were carried out with propylene oxide Manufacturing example tert. Amine Hydrocarbyl-substituted succinic acid 1 Cocoyldimethylamine Polyisobutylenesuccinic acid 2 Cocoyldimethylamine Tetrapropenylsuccinic acid 3 Cocoyldimethylamine i-Hexadecenyl / i-Octadecenylsuccinic acid 4 N-Methyl-N,N-Ditallow fatty amine Tetrapropenylsuccinic acid 6 nC 16 H 33 NMe 2 Polyisobutylenesuccinic acid 7 nC 16 H 33 NMe 2 Polyisobutylenesuccinic acid 8 nC 16 H 33 NMe 2 Polyisobutylenesuccinic acid 9 nC 16 H 33 NMe 2 Polyisobutylenesuccinic acid 10 nC 16 H 33 NMe 2 Polyisobutylenesuccinic acid 11 nC 16 H 33 NMe 2 Polyisobutylenesuccinic acid 12 nC 16 H 33 NMe 2 Polyisobutylenesuccinic acid 13 Cocoyldimethylamine Polyisobutylenesuccinic acid 16 N,N-Dimethylethanolamine*15 PO Tetrapropenylsuccinic acid 17 PIBSA-DMAPA succinimide Tetrapropenylsuccinic acid Notes on manufacturing example:

[0313] Nr. 7: 2-Propylheptanol was used as solvent instead of 2-ethylhexanol. Nr. 8: 2-Ethylhexanol / Solvent Naphtha ND 1:1 (w / w) was used as solvent instead of 2-ethylhexanol. Nr. 9: Ethylene oxide (1.5 eq.) was used instead of propylene oxide. 2-Propylheptanol was used as solvent instead of 2-ethylhexanol. Nr. 10: The PIBSA used (from maleic anhydride and polyisobutene 1000) had a bismaleination degree of 32% and a saponification number of 112.5 mg KOH / g. Nr. 11: 1.5 eq. of propylene oxide was used. Nr. 12: 1.1 eq. of propylene oxide was used. Nr. 13: 2-Propylheptanol was used as the solvent instead of 2-ethylhexanol. The PIBSA used (from maleic anhydride and polyisobutene 550) had a saponification number of 142.5 mg KOH / g. Nr. 16: 2-Propylheptanol was used as solvent, and a polyetheramine obtained by 15-fold propoxylation of N,N-dimethylethanolamine (preparation see synthesis example 1 of WO 2013 / 064689 A1) was used as amine. Nr. 17: 2-Propylheptanol was used as solvent, and the condensation product of polyisobutylenesuccinic acid (PIBSA) and DMAPA was used as amine, see Preparation Example 1 of WO 2013 / 000997 A1. Production example 5: Quaternization of trimethylamine with dodecenene oxide in the presence of tetrapropenylsuccinic acids Reagents: Dodecene oxide (CAS 2855-19-8) from Aldrich, Trimethylamine (anhydrous, CAS 75-50-3) from BASF

[0314] A solution of trimethylamine (47.2 g, 0.8 mol) and dodecene oxide (147.2 g, 0.8 mol) in 2-ethylhexanol (194.4 g) is placed in a 2-liter autoclave inertized with N 2 . The temperature is then increased to 40°C. A solution of tetrapropenylsuccinic acid (252.8 g, 0.8 mol) in 2-ethylhexanol (252.8 g) is added over the course of 1.5 h. The mixture is then stirred at 40°C for a further 15 h. Volatile components are removed by passing a stream of N 2 at 40°C, and the reactor is then emptied. 1< H-NMR (CDCl 3 ) confirms quaternization (δ = 3.3 ppm, singlet, RN(CH 3 ) 3 ). Preparation Example 14: Synthesis of iC 13 NMe 2

[0315] Tridecylamine (140.2 g) is initially introduced at room temperature, and formic acid (166.7 g) is added dropwise over 15 min with stirring. The reaction mixture is heated to 45°C, and aqueous formaldehyde solution (37%; 132.7 g) is added dropwise over 25 min with evolution of CO2. Stirring is then continued at 80°C for 23 h. After cooling to room temperature, hydrochloric acid (32%; 121.5 g) is added with stirring. The mixture is stirred for 3 h at room temperature, and the water is removed under vacuum using a rotary evaporator. 500 ml of water is added to the product mixture, and the amine is released using 50% sodium hydroxide solution. The mixture was extracted twice with methyl tert-butyl ether, the combined organic phases were dried over sodium sulfate, and the solvent was removed using a rotary evaporator. The product (143.5 g) showed a total amine value of 228 mg KOH / g with 94% tert. amine. Production example 15: Quaternization of iC 13 NMe 2 with propylene oxide / tetrapropenylsuccinic acid

[0316] According to the general synthesis procedure, iC 13 NMe 2 (Preparation Example 14), tetrapropenylsuccinic acid and propylene oxide were reacted in 2-propylheptanol instead of 2-ethylhexanol. Comparison example 1: Inventive Example 3 of GB 2496514

[0317] Dimethyloctadecyl(2-hydroxyhexyl)ammonium acetate is obtained by quaternization of nC 18 H 37 NMe 2 with hexene oxide / acetic acid. In contrast to all examples according to the invention, this product becomes cloudy when stored as a 50% solution in 2-ethylhexanol at room temperature for a period of 1 week. Comparison example 2: Quaternization of cocoyldimethylamine with propylene oxide / oleic acid

[0318] Analogous to the general synthesis procedure, a solution of cocoyldimethylamine (1 eq.) and oleic acid (1 eq.) in 2-ethylhexanol is placed in a 2 l autoclave. The amount of 2-ethylhexanol and the batch size are selected so that the final product has an active content of 50% and the reactor is filled to approximately 70%. The mixture is then purged three times with N 2 , an inlet pressure of approximately 2 bar N 2 is set, and the temperature is increased to 50°C. Propylene oxide (2 eq.) is added over the course of 1 h. The mixture is then stirred for a further 15 h at 50°C, cooled to 25°C, purged with N 2 , and the reactor is emptied. The product is transferred to a 2 l jacketed reactor and excess propylene oxide is removed by introducing a N 2 stream (10 l / h) under vacuum (70 mbar) at 50°C for 6 h. Comparison example 3: Quaternization of cocoyldimethylamine with propylene oxide / oleic acid

[0319] Analogous to the general synthesis procedure, a solution of cocoyldimethylamine (1 eq.) and oleic acid (2 eq.) in 2-ethylhexanol is placed in a 2 l autoclave. The amount of 2-ethylhexanol and the batch size are selected so that the final product has an active content of 50% and the reactor is filled to approximately 70%. The mixture is then purged three times with N 2 , an inlet pressure of approximately 2 bar N 2 is set, and the temperature is increased to 50°C. Propylene oxide (2 eq.) is added over the course of 1 h. The mixture is then stirred for a further 15 h at 50°C, cooled to 25°C, purged with N 2 , and the reactor is emptied. The product is transferred to a 2 l jacketed reactor and excess propylene oxide is removed by introducing a N 2 stream (10 l / h) under vacuum (70 mbar) at 50°C for 6 h. Analysis example 1 a) Determination of the degree of quaternization:

[0320] Quaternization levels are determined by 1< H NMR spectroscopy. For this purpose, the corresponding solvent is removed using a Kugelrohr distillation apparatus (60°C, p = 10 -3< mbar, 3 h). To determine the degree of quaternization, the alkyl moiety is compared with the signals of the quaternized product R CH 2 N Me 2 CH 2 CH(OH)R'. The quotients of the integrals of the signals of the quaternized product and the corresponding theoretical values ​​multiplied by 100% yield the degree of quaternization. The values ​​for the different signals are averaged. Residual solvent (doublet at δ = 3.55 ppm for HOC H 2 CHRR') are taken into account. Nr. Synthesis according to Degree of quaternization [%] 1 Comparison example 1 71 2 Comparison example 2 59 3 Production example 1 99 4 Production example 3 92 5 Production example 7 99 6 Production example 8 90 7 Production example 11 85 8 Comparison example 3 79

[0321] The 1< H NMR spectrum of Comparative Example 2 also shows a signal at δ = 3.98 ppm (dd, J = 1.0, 6.0 Hz), suggesting ester formation. Integration of the signal reveals the formation of 29% of the esterification product from oleic acid and propylene oxide. A signal at δ = 2.21 ppm (s) suggests unreacted cocoyldimethylamine.

[0322] The process according to the invention for quaternizing tertiary fatty amines with alkylene oxides in the presence of alkylidene succinic acids surprisingly provides significantly higher degrees of quaternization than the comparative examples in which monocarboxylic acids such as acetic acid or oleic acid are used. b) Thermogravimetry

[0323] For thermogravimetric analysis, the corresponding solvent was removed using a Kugelrohr distillation apparatus (60-70°C, p = 10 -3 < mbar, 3 h). Thermogravimetry was measured from 30°C to 900°C with a temperature increase of 20°C / min under a nitrogen atmosphere at a flow rate of 60 mL / min. The following mass changes (TG) at 350°C were determined: Nr Synthesis according to Mass change (TG) at 350°C 1 Production example 1 17% 2 Production example 7 34% C. Application examples:

[0324] In the following application examples, the additives are used either as pure substances (as synthesized in the above production examples) or in the form of an additive package. Application example 1: Determination of the additive effect on the formation of deposits in diesel engine injectors

[0325] DW10 test according to CEC F-098-08 Fuel: Summer diesel, without performance additives according to EN 590 B7 Part 1: Dirty up (YOU)Zn content in fuel: 3mg / kg, duration: 12 hours non-stop Power (t=0 h) = 98.2kW (at test start) Power (t=12 h) = 89.9 kW (at end of DU) Power loss (t = 12h) = 8.5% Part 2: Clean up (CU) Zn content in fuel: 1 mg / kg, duration: 6 hours non-stop Additive: 50 ppm active ingredient of additive according to preparation example 2 Power (t=0 h) = 89.2 kW (at start of test) Power (t=6 h) = 97.5 kW (at end of CU)

[0326] Based on the initial power value (98.2 kW), an increase in power from 90.8% to 99.3% is observed after 6 hours.

[0327] All data refer to ppm by weight (mg / kg), unless otherwise stated. Application example 2: DW10 Zn Motortest (clean up)

[0328] The test was conducted with a Peugeot DW10 engine, which was used according to the standard CEC F-98-08 procedure, but with a modified version using more severe conditions in the dirty-up section and a full-load run instead of the CEC F-98-08 procedure. The test consisted of two parts: I. Dirty up:

[0329] The more stringent conditions allow for significantly faster injector deposit formation and thus faster power loss determination than under standard CEC F-98-08 conditions: The engine was operated for 4.28 h at full load (4000 rpm) with base fuel according to EN590 B7, without performance additives containing 3 mg / kg Zn. The results are summarized in the following table.

[0330] The power loss in the DU is calculated as follows Powerloss , du % = 1 − Pend , du P 0 , du ∗ 100 II. Clean-up:

[0331] For clean-up test, shortened to 8 h according to CEC F-98-08 procedure with 1 ppm Zn in the form of a zinc didodecanoate solution and base fuel according to EN590 B7 fuel, without performance additives, containing additives according to the invention, the results summarized in the following table were obtained.

[0332] The power loss in the CU test is calculated as follows (a negative number for the power loss in the CU test means an increase in power) Powerloss DU CU % = Pend , du − pend , cu P 0 , du ∗ 100 test Addition Power before test, kW Power after test, kW Power loss, % Dirty up (accelerated procedure), full load 3 ppm Zn 98,3 92,9 5,5 Clean up, 8 hours, abbreviated procedure according to CEC F-98-08 1 ppm Zn and 33 ppm sample according to Preparation Example 1 93,0 96,4 -3,6 Dirty up (accelerated procedure), full load 3 ppm Zn 94,8 90,5 4,5 Clean up, 8 hours, abbreviated procedure according to CEC F-98-08 1 ppm Zn and 48 ppm sample according to Preparation Example 7 90,0 93,3 -3,0 Dirty up (accelerated procedure), full load 3 ppm Zn 94,7 90,8 4,1 Clean up, 8 hours, abbreviated procedure according to CEC F-98-08 1 ppm Zn and 60 ppm sample according to Preparation Example 7 90,4 94,5 -3,9 Dirty up (accelerated procedure), full load 3 ppm Zn 93,8 90,2 3,8 Clean up, 8 hours, abbreviated procedure according to CEC F-98-08 1 ppm Zn and 60 ppm sample according to Preparation Example 13 91,8 94,6 -4,7

[0333] The compounds described according to the invention are effective against the formation of deposits in direct injection engines, such as Peugeot DW10, when tested according to CEC F-98-08, and are able to remove the deposits formed earlier. Application example 3: XUD9 Motortest (keep clean)

[0334] The test was conducted according to the standard procedure CEC F-023-01 with a Peugeot XUD9 engine using diesel base fuel according to EN590 B7, without performance additives. Addition Flow reduction at 0.1 mm needle stroke, % No additive 76,8 20 ppm sample according to Preparation Example 1 67,3 100 ppm sample according to Preparation Example 1 19,5 24 ppm sample according to Preparation Example 3 46,7 36 ppm sample according to Preparation Example 3 24,0 36 ppm sample according to Preparation Example 7 46,8 24 ppm sample according to Preparation Example 6 52,0

[0335] The compounds described according to the invention are effective against the formation of deposits in indirect injection engines, such as Peugeot XUD9, when tested according to CEC F-023-01, and are able to remove the deposits formed earlier. Application example 4: CFPP EN 116 Test

[0336] The test was carried out according to the DIN EN 116 standard method for determining cold flow behavior (cold flow filter plugging point, CFPP) using winter diesel base fuel according to EN590 B7, without performance additives. Addition CFPP temperature according to EN 116, °C No additive -27 40 ppm sample according to Preparation Example 1 -28 80 ppm sample according to Preparation Example 1 -26 40 ppm sample according to Preparation Example 3 -27 120 ppm sample according to Preparation Example 3 -26 70 ppm sample according to Preparation Example 7 -29 80 ppm of sample according to Comparative Example 1 -22

[0337] The compounds described in this invention do not cause any deterioration of the cold flow properties and no deterioration of the CFPP value measured according to the EN 116 standard. Application example 5: Engine oil compatibility

[0338] The test was conducted according to the DGMK 531 1-A standard using base fuel according to EN590 B7 without performance additives and Wintershall Multi-Rekord Top 15W-40 engine oil. The product to be tested was mixed with engine oil and heated to 90 °C for 3 days. The mixture was then cooled and diluted with diesel fuel to a volume of 500 ml. The mixture was then filtered through a filter described in the procedure. A filtration time of more than 120 seconds was considered a failure. Addition in the test Filtration time, s Pass / fail 50% solution of sample according to Preparation Example 1 in ethylhexanol 105 Passed 50% solution of sample according to Preparation Example 3 in propylheptanol 120 Passed 50% solution of sample according to comparative example 1 >300 Failed, filter clogged

[0339] The compounds described according to the invention do not cause any deterioration in engine oil compatibility measured according to the DGMK 531 1-A standard and do not lead to a deterioration in engine oil properties. Application example 6: Corrosion protection test according to ASTM D665B (modified)

[0340] The test was conducted according to ASTM D665 B (modified) using water (artificial seawater) mixed with diesel base fuel according to EN590 B7, without performance additives.

[0341] The modifications were that the temperature was 60 °C and the duration of the test was 4 hours.

[0342] The test was evaluated according to the NACE classification. Both fuels with and without additives were tested. The results are presented in the following table. A 100% rust-proof B++ 0.1% or less of the total surface rusted B+ 0.1% - 5% of the total surface rusted B 5% - 25% of the total surface rusted C 25% - 50% of the total surface rusted D 50% - 75% of the total surface rusted E 75% - 100% of the total surface rusted Addition Evaluation in the ASTM D665B test (with artificial seawater) No additives E 70 ppm sample according to Preparation Example 3 A 70 ppm sample according to Preparation Example 1 A 70 ppm sample according to Preparation Example 6 A 70 ppm sample according to Preparation Example 7 A

[0343] The compounds described in the invention exhibit a very strong corrosion protection effect, as shown by ASTM D 665 B (using artificial seawater). Application example 7: DW10 Zn Motortest (keep clean)

[0344] The test was conducted using a Peugeot DW10 engine, following the standard 44-hour CEC F-98-08 procedure. A base fuel conforming to EN590 B7, without performance additives, was used in the tests. Both fuels with and without additives were tested. The results are summarized in the following table. Additives Performance loss after the test, % 1 ppm Zn 4,3 1 ppm Zn and 36 ppm sample according to Preparation Example 7 0

[0345] The compounds described in this invention are effective against the formation of deposits in direct injection engines such as the Peugeot DW10 as used in the test procedure according to CEC F-98-08 and are capable of removing previously formed deposits. Application example 8: HFRR DIN ISO 12156-1 Lubricity test

[0346] The test was conducted according to the DIN ISO 12156-1 standard for determining the lubricity of diesel fuels. The fuel was tested with and without additives. The abrasion was measured. The higher the abrasion, the poorer the lubricity properties of the fuel. Coryton B0 fuel with low lubricity was used in this test. Addition HFRR abrasion according to DIN ISO 12156-1 test, µm No additive 518 70 ppm sample according to Preparation Example 1 365

[0347] The compounds described according to the invention can improve the lubricity of diesel fuels and prevent malfunction of fuel pumps as measured in the DIN ISO 12156-1 test. Application example 9: DW10 Na Soap IDID test (clean up)

[0348] To investigate the influence of additives on the performance of direct-injection diesel engines, the IDID engine test was used as an additional test method. In this test, the exhaust gas temperatures of the cylinders at the cylinder outlet were determined during a cold start of the DW10 engine. A direct-injection diesel engine with a common rail system from Peugeot was used according to test methods CEC F-098-08. A commercially available B7 diesel fuel according to EN 590 was used as the fuel. To artificially stimulate deposit formation, 1 mg / L of sodium in the form of sodium naphthenate and 20 mg / L of dodecenylsuccinic acid were added.

[0349] Similar to the CEC F-98 -08 procedure, the engine power is measured during the test.

[0350] The test consisted of two parts: I. Dirty up:

[0351] The test was conducted without the addition of compounds according to this invention. The test was shortened to 8 hours; the CEC F-98-08 procedure was performed without the addition of Zn, but with the addition of sodium naphthenate and dodecylsuccinic acid (DDS). If significant deviations in exhaust temperatures were observed, the test was stopped before reaching the 8-hour mark to avoid engine damage. After the dirty-up run, the engine was allowed to cool and then restarted and operated at idle for 5 minutes. During these 5 minutes, the engine was warmed up. The exhaust temperature of each cylinder was recorded. The smaller the differences between the determined exhaust temperatures, the lower the amount of IDID formed.

[0352] The exhaust temperatures of the four cylinders ("Z1" to "Z4") were measured at the cylinder outlets after 0 minutes ("ϑ0") and after 5 minutes ("ϑ5"). The results of the exhaust temperature measurements, including average values ​​("Δ") and the largest deviations from Δ downwards ("-") and upwards ("+") for the two test runs, are summarized in the following overview. II. Clean-up:

[0353] The test was shortened to 8 hours, and the CEC F-98-08 method was performed without the addition of Zn. However, 1 mg / L Na in the form of sodium naphthenate, 20 mg / L dodecenylsuccinic acid, and a compound according to the invention were added, and the engine performance was determined.

[0354] After the cleanup, the engine was cooled down and restarted. The exhaust temperature of each cylinder was recorded. The smaller the differences between the measured exhaust temperatures, the lower the amount of IDID formed.

[0355] The exhaust temperatures of the four cylinders ("Z1" to "Z4") were measured at the cylinder outlets after 0 minutes ("ϑ0") and after 5 minutes ("ϑ5"). The results of the exhaust temperature measurements, including average values ​​("Δ") and the largest deviations from Δ downwards ("-") and upwards ("+"), are summarized in the following overview. Dirty up - Clean up - Sequence 1: Dirty up

[0356] Significant deviations in exhaust gas temperatures were observed during the test, so it was stopped after 3 hours to avoid engine damage. After dirty up:

[0357] ϑ0 Z1: 40°C Z2: 35°C Z3: 32°C Z4: 48°C ϑ5 Z1: 117°C Z2: 45°C Z3: 47°C Z4: 109°C Δ: 79.5°C (+37.5°C / -32.5°C) Significant deviations from the mean and significant differences between the individual cylinders demonstrate the presence of IDID. Clean-up

[0358] After clean up with 150 ppm sample according to preparation example 1 in the presence of 1 mg / L Na + 20 mg / L dodecenylsuccinic acid: ϑ0 Z1: 42°C Z2: 42°C Z3: 29°C Z4: 34°C ϑ5 Z1: 85°C Z2: 86°C Z3: 57°C Z4: 53°C Δ: 70.3°C (-17.3°C / + 15.7°C)

[0359] The deviation from the mean value of the exhaust gas temperature is low, which indicates the removal of IDID.

[0360] The compounds described according to the invention are very effective against the formation of IDID in direct injection engines, as can be seen in the example of the Peugeot DW10, which is used in the test similar to the CEC F-98-08 procedure, but in the presence of 1 mg / L Na in the form of sodium naphthenate and 20 mg / L dodecenylsuccinic acid. Application example 10: DW10 Na power loss Test (clean up)

[0361] To investigate the effectiveness of the compounds of the invention against power loss caused by metals such as Na, K, Ca, and others (and not by Zn as described above), an IDID engine test was used as described above. During the dirty-up and clean-up runs, power was measured according to CEC F-098-08, with a shortened clean-up period as described above.

[0362] The power loss in the DU is calculated as follows Powerloss , du % = 1 − Pend , du P 0 , du ∗ 100

[0363] The power loss in the CU test is calculated as follows (a negative number for the power loss in the CU test means an increase in power) Powerloss DU CU % = Pend , du − pend , cu P 0 , du ∗ 100 test Addition Power before test, kW Power after test, kW Power loss, % Dirty up, 8 hours, procedure as described above 1 mg / L Na + 20 mg / L dodecenylsuccinic acid 97,6 92,3 5,4 Clean up, 8 hours, procedure as described above 1 mg / L Na + 20 mg / L dodecenylsuccinic acid and 150 ppm sample according to Preparation Example 1 91,6 93,0 -0,7

[0364] The compounds described in this invention are effective against the formation of deposits caused by metals other than Zn, such as Na, K, Ca, as shown by the above Na power loss test. Application example 11: Injector cleanliness (direct injection gasoline engine; DISI)

[0365] a) Products used in the following application tests: Test 1: no additive (base run) Test 2: C16-dimethylamine + PIB-succinic acid + PO (Production Example 7), 25 mg / kg active content Test 3: tridecyldimethylamine + dodecenylsuccinic acid + PO (Production Example 15), 25 mg / kg active content Test 4: dimethylethanolamine / 15PO + dodecenylsuccinic acid (Production Example 16), 25 mg / kg active content European RON 92 E0 gasoline was used in all tests. b) The tests were conducted according to the following procedure, originally described in US2013225463. Method: BASF in-house method Engine: 1.6-liter turbocharged four-cylinder Test duration: 60 hours Test results:

[0366] test Change 2< ) of the FR value 1< ) Appearance of the injector Test 1 (basic run) + 4,54% Fig. 2A Test 2 - 2,66% Fig. 2B Test 3 - 1,90% Fig. 2C Test 4 - 1,99% Fig. 2D 1)< : The FR value is a parameter recorded by the engine control system that correlates with the duration of the fuel injection process into the combustion chamber. The more pronounced the formation of deposits in the injector nozzles, the longer the injection duration and the higher the FR value. Conversely, the FR value remains constant or tends to decrease slightly if the injector nozzles remain free of deposits. 2)< : Change in the FR value in % compared to the FR value at the beginning of the test (the larger the positive values, the more deposits are formed in the injector and the greater the injector contamination).

[0367] The results shown demonstrate that the products described above in the examples according to the invention are suitable for preventing the formation of deposits in injectors of direct-injection gasoline engines and for removing previously formed deposits.

[0368] The disclosure of the publications cited herein is expressly incorporated by reference.

Claims

1. A fuel composition comprising, in a majority of a customary fuel, a proportion of at least one reaction product comprising a quaternized nitrogen compound, wherein the reaction product is obtainable by reacting a quaternizable nitrogen compound comprising at least one quaternizable, especially tertiary, amino group with a quaternizing agent which converts the at least one quaternizable, especially tertiary, amino group to a quaternary ammonium group, wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid.

2. The fuel composition according to claim 1, selected from middle distillate compositions, especially from diesel and in particular biodiesel fuel compositions.

3. The middle distillate fuel composition according to claim 2, comprising a mixture of middle distillate fuel and biofuel oil.

4. The middle distillate fuel composition according to claim 2 or 3, comprising biofuel oil in amounts of 1% to 30% by weight, especially of 3% to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil; especially based on alkyl esters of fatty acids; in particular lower alkyl esters, especially C1- to C4-alkyl esters, which are obtainable by transesterifying the glycerides which occur in vegetable and / or animal oils and / or fats, especially triglycerides, by means of lower alcohols.

5. The middle distillate fuel composition according to claim 4, wherein the alkyl ester of fatty acid is selected from sunflower methyl ester, palm oil methyl ester ("PME"), soya oil methyl ester ("SME") and especially rapeseed oil methyl ester ("RME").

6. The fuel composition as claimed in any of the preceding claims, wherein the quaternizable nitrogen compound is selected from: a) at least one alkylamine of the following general formula 3         RaRbRcN     (3) in which at least one of the Ra, Rb and Rc radicals is a straight-chain or branched, saturated or unsaturated C8-C40-hydrocarbyl radical, especially straight-chain or branched C8-C40-alkyl radical, and the other radicals are identical or different, straight-chain or branched, saturated or unsaturated C1-C6-hydrocarbyl radicals, especially C1-C6-alkyl radicals; or in which all the Ra, Rb and Rc radicals are identical or different, straight-chain or branched, saturated or unsaturated C8-C40-hydrocarbyl radicals, especially straight-chain or branched C8-C40-alkyl radicals; or in which the Ra, Rb and Rc radicals have identical or different short-chain alkyl radicals, especially straight-chain or branched alkyl groups having 1 to 7 or in particular 1 to 4 carbon atoms; b) at least one polyalkene-substituted amine comprising at least one quaternizable, especially tertiary, amino group; c) at least one polyether-substituted amine comprising at least one quaternizable, especially tertiary, amino group; and d) at least one reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising a nitrogen or oxygen atom and additionally comprising at least one quaternizable amino group; and e) mixtures thereof.

7. The fuel composition according to any of the preceding claims, wherein the quaternizing agent comprises an epoxide of the general formula 4 where the Rd radicals present therein are the same or different and are each H or a hydrocarbyl radical, the hydrocarbyl radical being an aliphatic or aromatic radical having 1 to 10 carbon atoms, and optionally additionally containing heteroatoms, such as O, N, NH or S in particular, in the chain thereof.

8. The fuel composition according to any of the preceding claims, wherein the free acid of the quaternizing agent is a hydrocarbyl-substituted C3-C28 dicarboxylic acid.

9. The fuel composition according to any of the preceding claims, wherein the hydrocarbyl substituent of the carboxylic acid has a number-average molecular weight (Mn) of 85 to 20 000 or is a polyalkylene radical having a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25.

10. The fuel composition according to any of the preceding claims, wherein the quaternizable tertiary amine is a compound of the formula 3 in which at least two of the Ra, Rb and Rc radicals are the same or different and are a straight-chain or branched C10-C20-alkyl radical, and the other radical is C1-C4-alkyl.

11. The fuel composition according to any of the preceding claims, wherein the quaternizing agent is selected from hydrocarbyl epoxides of the above general formula 4 in combination with a hydrocarbyl-substituted dicarboxylic acid.

12. The fuel composition according to any of the preceding claims, wherein the carboxylic acid is selected from malonic acid, succinic acid, glutaric acid, adipic acid and pimelic acid.

13. The fuel composition according to any of the preceding claims, wherein the quaternizable nitrogen compound is selected from at least one alkyl amine of the above general formula 3 in which the Ra, Rb and Rc radicals have identical or different short-chain alkyl radicals, especially straight-chain or branched alkyl groups having 1 to 7 or in particular 1 to 4 carbon atoms.

14. The fuel composition according to any of claims 1 to 12, wherein the quaternizable tertiary amine is selected from the group consisting of hydroxyalkyl-substituted primary, secondary and in particular tertiary monoamines and hydroxyalkyl-substituted primary, secondary and in particular tertiary diamines.

15. The fuel composition according to any of claims 1 to 12, wherein the quaternizable tertiary amine is a hydroxyalkyl-substituted monoamine selected from the group consisting of N-hydroxyalkylmonoamines, N,N-dihydroxyalkylmonoamines and N,N,N-trihydroxyalkylmonoamines.

16. The fuel composition according to any of claims 1 to 12, wherein the quaternizable tertiary amine is selected from the group consisting of ethanolamine, 3-hydroxy-1-propylamine, diethanolamine, diisopropanolamine, N-(2-hydroxyethyl)ethylenediamine, triethanolamine, 1-(3-hydroxypropyl)imidazole, tris(hydroxymethyl)amine, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 2-dimethylamino-1-ethanol and 4-diethylamino-1-butanol.