USE OF A REACTION PRODUCT UNDERSTANDING A QUATERNIZED NITROGEN COMPOUND, OR A FRACTION OF THE SAME T

专利摘要:
use of a reaction product, composed of quaternized nitrogen, process for preparing a quaternized nitrogen compound, additive concentrate, and, fuel composition or lubricant composition. the present invention relates to the use of quaternized alkyl amine nitrogen compounds as a fuel additive and lubricant additive, such as, more particularly, as a detergent additive; to reduce or avoid deposits in direct injection diesel engine injection systems, especially in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with fuel injection systems. common rail injection, 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 the operation of disi engines.
公开号:BR112014014305B1
申请号:R112014014305-6
申请日:2012-12-12
公开日:2020-09-15
发明作者:Markus Hansch；Harald Böhnke；Ludwig Völkel；Wolfgang Grabarse；Jan Strittmatter
申请人:Basf Se；
IPC主号:

专利说明:

[0001] The present invention relates to the use of quaternized alkyl amine nitrogen compounds as a fuel additive and lubricant additive, such as, more particularly, as a detergent additive; to reduce or avoid deposits in direct injection diesel engine injection systems, especially in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with fuel injection systems. common rail injection, 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 the operation of DISI engines. State of the art:
[0002] In direct-injection diesel engines, fuel is injected and distributed in an ultra-fine (nebulized) manner through a multiple-hole injection nozzle that directly reaches the engine's combustion chamber, instead of being introduced into an anterior chamber or turbulence chamber as in the case of the conventional diesel engine (chamber). The advantage of direct injection diesel engines is their high performance for diesel engines and yet low fuel consumption. In addition, these engines reach very high torque even at low speeds.
[0003] At present, essentially these methods are being used for fuel injection directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the pump nozzle system (unit injector system or unit pump), and the common rail system.
[0004] In the common rail system, diesel fuel is transported by a pump with pressures up to 2000 bar (200 MPa) to a high pressure line, the common rail. Continuing from the common rail, branch lines run to the different injectors which inject the fuel directly into the combustion chamber. Full pressure is always applied to the common rail, which allows for multiple injection or a specific injection form. In other injection systems, in contrast, only less variation in injection is possible. Injection on the common rail is essentially divided into three groups: (1.) pre-injection, by which essentially smoother combustion is achieved, such that loud combustion noises ("nailing") are produced and the engine appears to run in silence; (2.) main injection, which is responsible for a good torque profile; and (3.) post-injection, which especially guarantees a low NOx value. In this post-injection, the fuel is generally not burned, but instead vaporized by residual heat in the cylinder. The exhaust gas / fuel mixture formed is transported to the exhaust gas system, where the fuel, in the presence of suitable catalysts, acts as a reducing agent for NOX nitrogen oxides.
[0005] The variable, individual cylinder injection in the common rail injection system can positively influence the pollutant emission from the engine, for example, the emission of nitrogen oxides (NOX), carbon monoxide (CO) and especially of particulates (soot). This makes it possible, for example, that engines equipped with common rail injection systems theoretically meet the Euro 4 standard even without additional particulate filters.
[0006] In current common rail diesel engines, under particular conditions, for example, when fuels containing biodiesel or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds are used , deposits can form in the injector orifices, which adversely affect the fuel injection performance and thus affect the performance of the engine, that is, especially reduce power, but in some cases also worsen combustion. The phonation of the deposits is further improved through additional developments in the construction of the injector, especially by changing the nozzle geometry (narrower, tapered holes with rounded outlet). For the long-lasting optimum operation of the engine and injectors, such deposits in the nozzle orifices must be avoided or reduced by suitable fuel additives.
[0007] In modern diesel engine injection systems, deposits cause significant performance problems. It is common knowledge that such deposits in the spray channels can lead to a decrease in fuel flow and thus to a loss of power. The deposits at the injector tip, in contrast, affect the optimal formation of the fuel spray mist and, as a result, cause worsened combustion and higher associated emissions and increased fuel consumption. In contrast to these conventional “external” deposition phenomena, “internal” deposits (collectively referred to as internal diesel injector deposits (IDID)) on particular parts of the injectors, such as the nozzle needle, control piston, piston valve, valve seat, control unit and guides of these components, also increasingly cause performance problems. Conventional additives exhibit inadequate action against these IDIDs.
[0008] US 4,248,719 describes quaternized ammonium salts which are prepared by reacting an alkenyl succinimide with a monocarboxylic ester and find use as lubricant oil dispersants for preventing sludge formation. More particularly, for example, the reaction of polyisobutyl succinic anhydride (PIBSA) with N, N-dimethylaminopropylamine (DMAPA) and quaternization with methyl salicylate is described. However, use in fuels, more particularly diesel fuels, is not proposed therein. The use of PIBSA with low levels of bismaleation less than 20% is not described therein.
[0009] US 4,171,959 describes quaternized ammonium salts of hydrocarbyl substituted succinimides, which are suitable as detergent additives for gasoline fuel compositions. Quaternization is preferably achieved using alkyl halides. Organic C2 to C8 hydrocarbyl sulfonates and carboxylates are also mentioned. Consequently, the quaternized ammonium salts provided according to the teachings therein have, as a counter ion, both a halide and a C2 to C8 hydrocarbyl carboxylate group or a C2 to C8 hydrocarbyl sulfonate group. The use of PIBSA with low levels of bismaleation below 20% is likewise not described therein.
[0010] EP-A-2 033 945 describes cold flow enhancers which are prepared by specific quaternization monoamines that support at least one Cs to C40 alkyl radical with a C1 to C4 alkyl ester of specific carboxylic acids. Examples of such carboxylic esters are dimethyl oxalate, dimethyl maleate, dimethyl phthalate and dimethyl fumarate. The different uses for enhancing the CFPP value of middle distillates are not demonstrated in EP-A-2 033 945.
[0011] WO 2006/135881 describes quaternized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and a compound containing an oxygen or nitrogen atom with a tertiary amino group, and subsequent quaternization by means of epoxide hydrocarbyl in the presence of stoichiometric amounts of an acid such as, more particularly, acetic acid. Suitable quaternizing agents claimed in WO 2006/135881 are dialkyl sulfates, benzyl halides and hydrocarbyl substituted carbonates, and dimethyl sulfate, benzyl chloride and dimethyl carbonate have been studied in an experimental manner.
[0012] The quaternizing agents used preferably in WO 2006/135881, however, have serious disadvantages such as: toxicity or carcinogenicity (for example, in the case of dimethyl sulfate and benzyl halides), no combustion of free residue ( example, in the case of dimethyl sulfate and alkyl halides), and inadequate reactivity that leads to incomplete quaternization or uneconomical reaction conditions (long reaction times, high reaction temperatures, excess of quaternization agent; case of dimethyl carbonate).
[0013] EP-A-2 033 945 describes the preparation of sulfur-free and halogen-free quaternary ammonium salts of organic carboxylic acids (for example, oxalic acid, phthalic acid, salicylic acid, malonic acid and maleic acid, and alkyls esters) and its use to improve the CFPP value of diesel fuels.
[0014] Quaternary ammonium salts of alpha-hydroxycarboxylic acids are proposed in EP-A-1 254 889 as cleaning agents for electronic components.
[0015] In addition, the Japanese patent application, under application number 61-012197, describes the use of quaternary ammonium salts of organic carboxylic acids as surfactants or essential materials for medicines or cosmetics.
[0016] Therefore it was an objective of the present invention to provide additional fuel additives that prevent deposits at the injector tip and additional injector deposits in the course of operation of common rail diesel engines. Brief description of the invention:
[0017] It was found that, surprisingly, the objective above is achieved by providing quaternized hydrocarbilamine compounds and fuel and lubricant compositions added with it.
[0018] Surprisingly, the additives of invention, as illustrated more particularly by the accompanying usage examples, are surprisingly effective in common rail diesel engines and are notable for particular stability as an additive to reduce power loss resulting external deposits and cold start problems that result from internal deposits. Description of figures:
[0019] Figure 1 shows a measurement of the time-dependent change (h) in the exhaust gas temperatures of the cylinders in the case of using a fuel without additive; large temperature deviations are caused by additional injector deposits.
[0020] Figure 2 shows the time-dependent change (h) in the exhaust gas temperatures in the same cylinders as in figure 1, but now after treatment with the additive of invention from preparation example 3, dosage of 394 mg / kg.
[0021] Figure 3 shows the profile of a one-hour engine test cycle for CEC F-098-08. Detailed description of the invention: A1) Specific embodiments
[0022] The present invention relates in particular to the following specific embodiments: 1. A fuel composition or lubricant composition comprising, in most of a common lubricant or fuel, a proportion, especially an effective amount, of at least one product reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product which can be obtained by reaction of an alkyl amine which can be quaternized comprising at least one tertiary amino group which can be quaternized with a quaternizing agent which converts at least one tertiary amino group to a quaternary ammonium group, The quaternizing agent being the alkyl ester of a cycloaliphatic monocarboxylic or polycarboxylic acid or cycloaromatic, especially of a monocarboxylic or dicarboxylic acid, or an aliphatic polycarboxylic acid, especially dicarboxylic acid, a hydrocarbyl epoxide, optionally in combination with a free acid, or a dialkyl carbonate such as di-C 1 -C 4 carbonate, especially dimethyl carbonate. 2. The fuel composition or lubricant composition according to embodiment 1, wherein the alkyl amine comprises at least one compound of the following general formula 3 RaRbRcN (3) in which at least one of the radicals Ra, Rb and Re , for example, one or two, is a straight or branched chain saturated or unsaturated C8 to C40 hydrocarbyl radical (especially straight or branched chain Cg to C40 alkyl) and the remaining radicals are identical or different, hydrocarbyl radicals from Ci to C6 saturated or unsaturated from a straight or branched chair (especially C1 to C6 alkyl); OR 2a. The fuel composition or lubricant composition according to embodiment 1, wherein the alkyl amine comprises at least one compound of the following general formula 3 RaRbRcN (3) in which all the radicals Ra, Rb and Rc are identical or different , straight or branched chain saturated or unsaturated Cg to C4o hydrocarbon radicals, especially straight or branched chain Cg to C4o alkyl radicals. 3. The fuel composition or lubricant composition according to any of the preceding embodiments, wherein the quaternizing agent is a compound of the general formula 1 R1OC (O) R2 (1) in which Ri is a hydrocarbon radical of low molecular weight such as alkyl or alkenyl radical, especially a lower alkyl radical such as, more particularly, methyl or ethyl, and R2 is an optionally substituted monocyclic hydrocarbon radical, especially an aryl or cycloalkyl or cycloalkenyl radical, especially aryl such as phenyl, where the substituent is selected from OH, NH2, NO2, C (O) ORB, and RiOC (O) -, where Ri is as defined above and R3 is H or Ri, where 0 substituent is especially OH. More particularly, the quaternizing agent is phthalate or salicylate, such as dimethyl phthalate or methyl salicylate. 4. The fuel composition according to any one of embodiments 1 and 2, wherein the quaternizing agent is a compound of the general formula 2 R1OC (O) -AC (O) OR1a (2) in which each of Ri and Ria is independently a low molecular weight hydrocarbon radical such as an alkyl or alkenyl radical, especially a lower alkyl radical, and A is an optionally monosubstituted or polysubstituted hydrocarbene (such as, more particularly, a C1 to C7 alkylene or a C2a C7 alkenylene optionally monosubstituted or polysubstituted); where suitable substituents, for example, are selected from OH, NH2, NO2, or C (O) ORs, especially OH and C (O) ORs, where R3 is as defined above. 5. The fuel composition or lubricant composition according to any one of embodiments 1 and 2, 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, where the hydrocarbyl radical is an aliphatic or aromatic radical having at least 1 to 10 carbon atoms and the free acid of the quaternizing agent is one free protic acid, especially a Ci to Cn monocarboxylic acid, Ci to C12 dicarboxylic acid or Ci aC 12 oligocarboxylic acid. 6. The fuel composition or lubricant composition according to any of the previous embodiments, wherein the tertiary amine that can be quaternized is a compound of the formula 3 in which at least one of the radicals Ra, Rb and Rc are the same or different and each is a straight or branched chain C1 to C20 alkyl radical and the other radical is a C1 to C4 alkyl. 7. The fuel composition or lubricant composition according to any of the foregoing embodiments, wherein the quaternizing agent is selected from lower alkylene oxides in combination with a monocarboxylic acid, alkyl salicylates, dialkyl phthalates and dialkyl oxalates. 8. The fuel composition or lubricant composition according to any of the previous embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels, and gasoline fuels that contain alkanol, such as fuels that contain bioethanol, especially diesel fuels. 9. A quaternized nitrogen compound as defined in any of embodiments 1 to 7. 10. A process for preparing a quaternized nitrogen compound according to embodiment 9, comprising the reaction of an alkyl amine that can be quaternized comprising at least one tertiary amino group that can be quaternized with a quaternizing agent that converts at least one tertiary amino group to a quaternary ammonium group, quaternizing agent being the alkyl ester of a cycloaliphatic or cycloaromatic monocarboxylic or polycarboxylic acid, especially of a monocarboxylic or dicarboxylic acid, or an aliphatic polycarboxylic acid, especially dicarboxylic acid, or a hydrocarbyl epoxide in combination with an acid. 11. The use of a nitrogen compound quantized according to embodiment 9 or prepared according to embodiment 10 as a fuel additive or lubricant additive. 12. The use according to embodiment 11 as an additive to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with common rail injection systems, and / or to minimize power loss on direct injection diesel engines, especially on diesel engines with common rail injection systems (for example, determined in a DW10 test based on CEC F-098-08, as described in detail in the experiments below). 13. The use according to embodiment 11 as a gasoline fuel additive to reduce the level of deposits in the intake system of a gasoline engine, such as, more particularly, DISI and PFI (fuel injector) engines. door). 14. The use according to embodiment 10 as a diesel fuel additive to reduce and / or prevent deposits in the injection systems, for example, determined in an XUD 9 test for CEC-F-23-1-01, such as, more particularly, internal diesel injector deposits (IDIDs), and / or valve grip on direct injection diesel engines, especially in common rail injection systems (for example, determined by a IDID as described in detail in the experiments below). 15. An additive concentrate comprising, in combination with diesel fuel additives or gasoline fuel additives or additional lubricant additives, at least one quaternized nitrogen compound as defined in embodiment 9 or prepared according to embodiment 10.
[0023] Appropriate test methods for examining each of the applications designated above are known to those skilled in the art, or are described in the experiments that follow, which are explained and general reference is made here. A2) General definitions
[0024] In the absence of statements to the contrary, the following general definitions apply.
[0025] "Hydrocarbyl" can be quite interpreted and comprises both straight or branched hydrocarbyl radicals of long or short chain having 1 to 50 carbon atoms, which can optionally additionally comprise hetero atoms, for example, O, N, NH, S, in the same chain. A specific group of hydrocarbon radicals comprises both straight or branched long-chain or short-chain alkyl radicals having 1 to 50 carbon atoms.
[0026] "Long-chain" hydrocarbyl radicals are straight-chain or branched hydrocarbyl radicals and have 7 to 50 or 8 to 50 or 8 to 40 or 10 to 20 carbon atoms, which can optionally additionally comprise hetero atoms, for example, O , N, NH, S, in the same chain. In addition, the radicals can be monounsaturated or polyunsaturated and have one or more, for example, 1 to 5, such as 1, 2 or 3, double CC bonds or triple CC bonds, especially 1, 2 or 3 bonds doubles. They can be of natural or synthetic origin. They can also have a numerical average molecular weight (Mn) of 85 to 20,000, for example, 113 to 10,000, or 200 to 10,000 or 350 to 5000, for example, 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. In this case, they are more particularly formed essentially from C1 to C6 monomer units, especially C2 to C4 such as ethylene, propylene, n-butylene or isobutylene or mixtures thereof, where the different monomers can be copolymerized in distribution random or as blocks. Such long-chain hydrocarbon radicals are also referred to as polyalkylene radicals or poly-C1 to C4-alkylene or P10-C2 to C4-alkylene radicals. Suitable long-chain hydrocarbon radicals and their preparation are also described, for example, in WO 2006/135881 and the literature cited therein. A specific group of long chain hydrocarbon radicals comprises straight or branched alkyl radicals ("long chain" alkyl radicals) having 8 to 50, for example, 8 to 40 or 8 to 30 or 10 to 20, carbon atoms.
[0027] "Short chain hydrocarbyl" or "low molecular weight hydrocarbyl" is especially straight or branched alkenyl or alkyl, optionally interrupted by one or more, for example, 2, 3 or 4, heteroatom groups such as - O- or -NH-, or optionally monosubstituted or polysubstituted, for example, disubstituted, trisubstituted, or tetra-substituted.
[0028] "Hydrocarbilene" represents straight-chain or single-branched or multiple-branched linking groups having 1 to 10 carbon atoms, optionally interrupted by one or more, for example, 2, 3 or 4, heteroatom groups such as - O- or -NH-, or optionally monosubstituted or polysubstituted, for example, disubstituted, trisubstituted, or tetra-substituted.
[0029] "Alkyl" or "lower alkyl" especially represents saturated straight or branched chain hydrocarbon radicals having 1 to 4, 1 to 5, 1 to 6, or 1 to 7, carbon atoms, for example, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 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; and also n-heptyl, and analogues with one branch or multiple branches thereof.
[0030] "Long chain alkyl" especially represents saturated straight or branched chain hydrocarbon radicals having 8 to 50, for example, 8 to 40 or 8 to 30 or 10 to 20, carbon atoms such as octyl, nonyl, decyl , undecil, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecil, eicosil, hencosil, docosil, tricosil, tetracosil, pentacosil, hexacosil, heptacosil, octacosil, especially isomeric, isomeric, isomeric, isomeric; with multiple branches and superior counterparts of the same.
[0031] "Alkenyl" represents monounsaturated straight or branched chain hydrocarbons, especially monounsaturated or polyunsaturated having 2 to 4, 2 to 6 or 2 to 7 carbon atoms and a double bond in any position, for example, C 2 to C 6 alkenyl such as ethylene, 1-propenyl , 2-propenyl, 1-methylethyl, 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-me tyl-3-pentenyl, 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- l-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-l-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-l- butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,2-2-trimethyl- 2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.
[0032] "Alkylene" represents straight chain hydrocarbon bonding groups with one or more branches having 1 to 10 carbon atoms, for example, C 1 to C alkylene groups; selected from -CH2-, - (CH2) 2-, - (CH2) 3-, -CH2-CH (CH3) -, -CH (CH3) -CH2-, - (CH2) 4-, - (CH2 ) 2- CH (CH3) -, -CH2-CH (CH3) -CH2-, (CH2) 4-, - (CH2) 5-, - (CH2) Ó, - (CH2) 7-, - CH (CH3 ) -CH2-CH2-CH (CH3) - OR -CH (CH3) -CH2-CH2-CH2-CH (CH3) - OR C1 to C4 alkylene groups selected from -CH2-, - (CH2) 2- , - (CH2) 3-, -CH2-CH (CH3) -, -CH (CH3) -CH2-, - (CH2) 4-, - (CH2) 2-CH (CH3) -, -CH2- CH ( CH3) -CH2-,
[0033] "Alkenylene" represents monounsaturated or polyunsaturated, especially monounsaturated, analogues of the above alkylene groups having 2 to 10 carbon atoms, especially C2-C7-alkenyls or C2-C4-alkenylene, such as -CH = CH- , -CH = CH-CH2 -, - CH2-CH = CH-, - CH = CH-CH2-CH2-, -CH2-CH = CH-CH2-, -CH2-CH2-CH = CH-, -CH ( CH3) - CH = CH-, -CH2-C (CH3) = CH-,
"Cycloalkyl" represents carbocyclic radicals having 3 to 20 carbon atoms, for example, C3 to C12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference is given to cyclopentyl, cyclohexyl, cycloheptyl, and also cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl on cycloalkyl C3 to C7 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, heptyl, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylethyl, cyclohexylmethyl, where the bond with the rest of the molecule can be through any suitable carbon atom.
[0035] "Aryl" represents optionally substituted aromatic radicals, monocyclic or polycyclic, preferably monocyclic or bicyclic having 6 to 20, for example, 6 to 10, ring carbon atoms, for example, phenyl, biphenyl, naphthyl such as 1- naphthyl or 2-naphthyl, tetrahydronaphthyl, fluorenyl, indenyl and phenanthrenyl. These aryl radicals can optionally support 1, 2, 3, 4, 5 or 6 identical or different substituents.
[0036] "Substituents" for the radicals specified here are especially, unless otherwise stated, selected from keto, -COOH, -COO-alkyl, -OH, -SH, -CN, amino, groups - NO2, alkyl, or alkenyl groups.
[0037] "Mn" represents the numerical average molecular weight and is determined in a conventional manner; more particularly, such statements refer to the Mn values determined by gel permeation chromatography. A3) Tertiary amines of the formula (3)
[0038] The tertiary amines of formula (3) are compounds known per se, as described, for example, in EP-A-2 033 945.
[0039] The tertiary amine reagent (3) preferably supports a segment of the formula NRaRb where one of the radicals has an alkyl group having 8 to 40 carbon atoms and the other an alkyl group having up to 40 and more preferably 8 to 40 atoms carbon. The Rc radical is especially a lower alkyl of C1 to C6 radical, such as a methyl, ethyl or propyl group. Ra and Rb can be straight or branched, and / or they can be the same or different. For example, Ra and Rb can be a straight chain C12 to C24 alkyl group. Alternatively, only one of two radicals can be long-chain (for example, having 8 to 40 carbon atoms), and the other can be a methyl, ethyl or propyl group.
[0040] Appropriately, the NRaRb segment is derived from a secondary amine, such as dioctadecylamine, dicocoamine, hydrogenated di-sebum amine and methylbehenylamine. Mixtures of amines as can be obtained from natural materials are likewise suitable. An example is a secondary hydrogenated tallow amine where the alkyl groups are derived from hydrogenated tall oil, and contains about 4% by weight of CM, 31% by weight of CM and 59% by weight of Cl8 alkyl groups. Corresponding tertiary amines of formula (3) are sold, for example, by Akzo Nobel under the name Armeen® M2HT or Armeen® M2C.
The tertiary amine reagent (3) can also take such a shape that the radicals Ra, Rb and Rc have identical or different long chain alkyl radicals, especially straight or branched alkyl groups having 8 to 40 carbon atoms.
[0042] Additional non-limiting examples of suitable amines are: N, N-dimethyl-N- (2-ethylhexyl) amine, N, N-dimethyl-N- (2-propylheptyl) amine, dodecyl-dimethylamine, hexadecyl dimethylamine, oleyldimethylamine, cocoyldimethylamine, dicocoylmethylamine, tallow dimethylamine, tallow dimethylamine, tridodecylamine, trihexadecylamine, trioctadecylamine, soy dimethylamine, tris (2-ethylhexyl) amine, and alamine 336 (tri). A4) Quaternization agent:
[0043] Quatizing agents useful in principle include all suitable compounds in this way, the quaternizing agent is specially selected from alkylene oxide, optionally in combination with acid; aliphatic or aromatic carboxyl esters such as, more particularly, dialkyl carboxylates; alkanoates; aromatic or non-aromatic cyclic carboxylic esters; alkyl sulfates; alkyl halides; alkylaryl halides; dialkyl carbonates; and mixtures thereof.
Suitable examples are alkyl esters, derived from carboxylic acids, which pKa is less than 3.5. Examples are especially alkyl esters derived from oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid and citric acid.
[0045] In a particular embodiment, however, the at least one tertiary nitrogen atom that can be quaternized is quaternized with at least one quaternizing agent selected from a) compounds of the general formula 1 R1OC (O) R2 (1) where Ri is a lower alkyl radical and R2 is an optionally substituted monocyclic cycloalkyl or aryl radical, where the substituent is selected from OH, NH2, NO2, C (O) ORa; RiaOC (O) - where Ria is as defined above for Ri, and R3 is H or Ri; or b) compounds of the general formula 2 R1OC (O) -A-C (O) OR1a (2) in which each of Ri and Ria is independently a lower alkyl radical and
[0046] A is an optionally monosubstituted or polysubstituted hydrocarbilene (such as, more particularly, a C1 to C7 alkylene or an optionally monosubstituted or polysubstituted C2a alkenylene); where suitable substituents, for example, are selected from OH, NH2, NO2, or C (O) OR2, especially OH and C (O) ORs, where R3 is as defined above.
[0047] Particularly suitable compounds of formula 1 are those in which R1 is a C1, C2 or C3 alkyl radical and R2 is a substituted phenyl radical, where the substituent is HO- or an ester radical of the formula RiaOC (O) - which is position for, meta or especially ortho for the radical RiOC (O) - in the aromatic ring.
Especially suitable quaternizing agents are lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate.
[0049] Esters mentioned above are typically used in the presence of acids, especially in the presence of free protic acids such as, in particular, with Ci to Ci2 monocarboxylic acids such as formic acid, acetic acid or propionic acid, or C2 dicarboxylic acids C12 such as oxalic acid or adipic acid; or even in the presence of sulfonic acids such as benzene sulfonic acid or toluene sulfonic acid, or aqueous mineral acids such as sulfuric acid or hydrochloric acid.
[0050] c) In a particular additional embodiment, at least one tertiary nitrogen atom that can be quaternized is quaternized with at least one quaternizing agent selected from epoxides, especially hydrocarbon epoxides.
where the Rd radicals present therein are the same or different and are each H or a hydrocarbyl radical, where the hydrocarbyl radical has at least 1 to 10 carbon atoms. These are especially aliphatic or aromatic radicals, for example, linear or branched C 1 to C 10 alkyl radicals, or aromatic radicals such as C 1 to C 4 alkyl phenyl or alkyl phenyl.
[0051] Examples of suitable hydrocarbon epoxides include aliphatic and aromatic alkylene oxides such as, more particularly, C2 to C12 alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2-oxide , 3-butylene, 2-methyl-1, 2-propene oxide (isobutene oxide), 1,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2,2-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, 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, especially styrene oxide or 4-methylstyrene oxide.
[0052] In the case of the use of epoxides as quaternizing agents, these are used in the presence or absence of free acids, especially in the presence or absence of free protic acids, such as, in particular, with Ci to Cn monocarboxylic acids such as formic acid, acetic acid or propionic acid, or C2 to C12 dicarboxylic acids such as oxalic acid or adipic acid; or even in the presence or absence of sulfonic acids such as benzene sulfonic acid or toluene sulfonic acid, or aqueous mineral acids such as sulfuric acid or hydrochloric acid. The quaternization product prepared in this way can either "contain acid" or be "acid free" in the context of the present invention. A5) Preparation of additives of the invention: a) Quaternization
[0053] Quaternization is carried out in a manner known per se. (1) To perform the quaternization, the tertiary amine is mixed with at least one compound of the above formula 1 or 2, especially in the stoichiometric amounts necessary to achieve the desired quaternization. It is possible, for example, to use 0.1 to 5.0, 0.2 to 3.0 or 0.5 to 2.5 equivalents of quaternizing agent per tertiary nitrogen atom equivalent that can be quaternized. More particularly, however, about 1 to 2 equivalents of quaternizing agent are used in relation to the tertiary amine, in order to completely quaternize the tertiary amine group. Typical working temperatures here are in the range from 50 to 180 ° C, for example, 90 to 160 ° C or 100 to 140 ° C. The reaction time can be in the region of a few minutes or a few hours, for example, about 10 minutes to about 24 hours. The reaction can be carried out at a pressure of about 0.1 to 20 bar (0.01 MPa to 2 MPa), for example, 1 to 10 or 1.5 to 3 bar (0.1 to 1 or 0.15 or 0.3 MPa), but especially around the standard pressure. If necessary, the reagents can be loaded initially for quaternization in a suitable inert organic aromatic or aliphatic solvent or a mixture thereof. Typical examples are, for example, solvents of the solvesso series, toluene or xylene, or ethylhexanol. The quaternization can, however, also be carried out in the absence of a solvent. To perform quaternization, adding catalytically active amounts of an acid may be appropriate. Preference is given to aliphatic monocarboxylic acids, for example, Cl to Cl8 monocarboxylic acids such as, more particularly, lauric acid, isononanoic acid or 3,3,5-trimethylhexanoic acid or neodecanoic acid, but also aliphatic or dicarboxylic acids polybasic aliphatic carboxylic acids with a carbon atom number in the range specified above. Quaternization can also be performed in the presence of a Lewis acid. However, quaternization can also be carried out in the absence of any acid. (2) The quaternization with an epoxide of the formula (4) is carried out in the same way in a manner known per se. When the boiling temperature of a component of the reaction mixture, especially epoxide, at standard pressure is above the reaction temperature, the reaction is carried out properly in an autoclave.
[0054] For example, in an autoclave, a solution of the tertiary amine is mixed with the organic acid (for example, acetic acid) in the required stoichiometric amounts. It is possible to use, for example, 0.1 to 2.0, 0.2 to 1.5 or 0.5 to 1.25 equivalents of acid per equivalent of tertiary nitrogen atom that can be quatemized. More particularly, however, approximately equimolar proportions of the acid are used. This is followed by sufficient purging with N2, and establishment of an adequate initial pressure, and metered addition of epoxide (eg, propylene oxide) in the required stoichiometric amounts at a temperature between 20 ° C and 180 ° C. It is possible to use, for example, 0.1 to 4.0, 0.2 to 3 or 0.5 to 2 epoxide equivalents per tertiary nitrogen atom equivalent that can be quatemized. More particularly, however, about 1 to 2 epoxide equivalents are used in relation to the tertiary amine, in order to completely quaternize the tertiary amine group. This is followed by stirring over a suitably long period of a few minutes to about 24 hours, for example, about 10 h, at a temperature between 20 ° C and 180 ° C (for example 50 ° C), cooling for example, up to about 20 to 50 ° C, purging with N2 and emptying the reactor.
[0055] The reaction can be carried out at a pressure of about 0.1 to 20 bar (0.01 to 2 MPa), for example, 1 to 10 or 1.5 to 5 bar (0.1 to 1 or 0 , 15 or 0.3 MPa). However, the reaction can also be carried out at standard pressure. An atmosphere of inert gas is particularly suitable, for example, nitrogen.
[0056] If necessary, the reagents can be initially loaded for quaternization in a suitable inert organic aromatic or aliphatic solvent or a mixture thereof. Typical examples are, for example, solvents from the Solvesso series, toluene or xylene, or 2-ethylhexanol. Quaternization, however, can also be performed in the absence of a solvent.
[0057] 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 especially have a dielectric constant (at 20 ° C) of more than 7. The protic solvent can comprise one or more OH groups, and it can also be water. Suitable solvents can also be alcohols, glycols and glycol ethers. More particularly, suitable protic solvents can be those specified in WO 2010132259. Especially suitable solvents are methanol, ethanol, n-propanol, isopropanol, all butanol isomers, all pentanol isomers, all hexanol isomers, 2-ethyl- hexanol, 2-propyl-heptanol, and also mixtures of different alcohols. The presence of a protic solvent can also positively influence the conversion and reaction rate of quaternization. b) Processing of the reaction mixture
[0058] The final reaction product formed so theoretically can be further purified, or the solvent can be removed. Optionally, excess reagent, for example, excess epoxide, can be removed. This can be achieved, for example, by introducing nitrogen under standard pressure or under reduced pressure. In order to improve the processing capacity of the products, however, it is also possible to add solvents after the reaction, for example, 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 without further purification as an additive, optionally after mixing with additional additive components (see below). B) Additional additive components Fuel with additives with the quantized additive of the invention is a gasoline fuel or especially a medium distillate fuel, in particular a diesel fuel. fuel can comprise additional common additives to improve efficiency and / or suppress wear.
[0059] In the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow enhancers, lubrication enhancers, corrosion inhibitors, demulsifiers, deterrent agents, defoamers, cetane number enhancers, fuel enhancers combustion, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.
[0060] In the case of gasoline fuels, these are in particular lubrication enhancers (friction modifiers), corrosion inhibitors, demulsifiers, distorting agents, defoamers, combustion enhancers, antioxidants or stabilizers, antistatic agents, metallocenes, deactivators metal, dyes and / or solvents.
[0061] Typical examples of suitable coadditives are listed in the following section: B1) Detergent additives
[0062] Common detergent additives are preferably amphiphilic substances having at least one hydrophobic hydrocarbon radical with a numerical average molecular weight (Mn) of 85 to 20,000 and at least one polar portion selected from: (Da) monoamino or polyamine groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties; (Db) nitro groups, optionally in combination with hydroxyl groups; (Dc) hydroxyl groups in combination with monoamino or polyamino groups, at least one nitrogen atom having basic properties; (Dd) carboxyl groups or the alkali metal or alkaline earth metal salts thereof; (De) sulfonic acid groups or the alkali metal or alkaline earth metal salts thereof; (Df) polyoxy-C2 to C4-alkylene moieties terminated by hydroxyl groups, monoamino or polyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups; (Dg) carboxylic ester groups; (Dh) portions derived from succinic anhydride and having hydroxyl and / or amino and / or starch and / or imido groups; and / or (Di) portions obtained by Mannich reaction of phenols substituted with aldehydes and monoamines or polyamines.
[0063] The hydrophobic hydrocarbon radical in the detergent additives above, which ensures adequate solubility in the fuel, has a numerical average molecular weight (Mn) of 85 to 20,000, preferably 113 to 10,000, more preferably 300 to 5000, even more preferably from 300 to 3000, even more especially preferably from 500 to 2500 and especially from 700 to 2500, in particular from 800 to 1500. As typical hydrophobic hydrocarbon radicals, especially in conjunction with polar radicals, especially polypropenyl, polybutenyl and polyisobutenyl with a numerical average molecular weight Mn of preferably in each case 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even more especially preferably 700 to 2500 and especially 800 to 1500 in consideration.
[0064] Examples of the above groups of detergent additives include the following:
[0065] Additives comprising monoamino or polyamino (Da) groups are preferably polyalkylene monoamines or polyalkene polyamines based on polypropene or in high reactivity (i.e. having predominantly double terminal bonds) or conventional (i.e. having predominantly internal double bonds) polybutene or polyisobutene having Mn = 300 to 5000, more preferably 500 to 2500 and especially 700 to 2500. Such additives based on high reactivity polyisobutene, which can be prepared from polyisobutene which can comprise up to 20% in weight of n-butene units by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylene diamine, diethylene triamine, triethylene tetramine or tetraethylene enepentamine, are especially known from EP-A 244 616. When polybutene or poly-isobuty predominantly internal doubles (commonly in the beg positions) are used as particle materials In the preparation of the additives, a possible preparation route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carboxyl or carbonyl compound and subsequent amination under reducing (hydrogenation) conditions. The amines used here for the amination can be, for example, ammonia, monoamines or the polyamines mentioned above. Corresponding additives based on polypropene are described more particularly in WO-A 94/24231.
[0066] Additional particular additives comprising monoamino (Da) groups are the hydrogenation products of the polyisobutene reaction products having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen and oxygen oxides, such as more particularly described in WO-A 97/03946.
[0067] Additional particular additives comprising monoamino (Da) groups are those compounds that can be obtained from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of amino alcohols, as described more particularly in DE-A 196 20 262.
[0068] Additives comprising nitro groups (Db), optionally in combination with hydroxyl groups, are preferably reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of oxides nitrogen and oxygen, as described more particularly in WO-A 96/03367 and WO-A 96/03479. These reaction products in general are mixtures of pure polyisobutene nitro (eg, α, β-dinitro polyisobutene) and mixed hydroxynitropolyisobutenes (eg α-nitro-β-hydroxypoly-isobutene).
[0069] Additives comprising hydroxyl groups in combination with monoamino or polyamino (Dc) groups are especially reaction products of polyisobutene epoxides which can be obtained from polyisobutene having preferably predominantly double terminal bonds and Mn = 300 to 5000 , with ammonia or monoamines or polyamines, as described more particularly in EP-A 476 485.
[0070] Additives comprising carboxyl groups or alkali metal or alkaline earth metal (Dd) salts are preferably copolymers of C2 to C40 olefins with maleic anhydride having a total molar mass of 500 to 20,000 and part of or all of the carboxyl groups were converted to the alkali metal or alkaline earth metal salts and any remaining carboxyl groups were reacted with alcohols or amines. Such additives are described more particularly by EP-A 307 815. Such additives serve primarily to prevent wear of the valve seat and can, as described in WO-A 87/01126, be advantageously used in combination with common fuel detergents such as poly (iso) butenoamines or polyether amines.
[0071] Additives comprising sulfonic acid groups or alkali metal or alkaline earth metal (De) salts are preferably alkali metal or alkaline earth metal salts of an alkyl sulfo succinate, as described more particularly in EP-A 639 632. Such additives mainly serve to prevent wear of the valve seat and can be used advantageously in combination with common fuel detergents such as poly (iso) butenoamines or polyether amines.
[0072] Additives comprising polyoxy-C2 to C4-alkylene (Df) moieties are preferably polyethers or polyether amines which can be obtained by reacting C2 to COC alkanols, C30 to C30 alkanediools, C2 to C30 monoalkyl amines or dialkyl amines C1 to C30 alkylcyclohexanol or C1 to C30 alkyl phenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyether amines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described more particularly 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 have carrier oil properties. Typical examples of these are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia.
[0073] Additives comprising carboxylic ester (Dg) groups are preferably esters of monocarboxylic acids, dicarboxylic acids or tricarboxylic acids with long chain alkanols or polyols, especially those having a minimum viscosity of 2 mm2 / s at 100 ° C, as more particularly described in DE-A 38 38 918. The monocarboxylic acids, dicarboxylic acids or tricarboxylic acids used can be aliphatic or aromatic acids, and particularly suitable alcohol esters or polyols are long-chain representatives that have, for example, 6 to 24 carbon atoms . Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellites of iso-octanol, isononanol, isodecanol and isotridecanol. Such products also satisfy the properties of carrier oil.
[0074] Additives comprising portions derived from succinic anhydride and having hydroxyl and / or amino and / or starch and / or especially imido (Dh) groups are preferably corresponding derivatives of alkyl or alkenyl substituted succinic anhydride and especially the corresponding derivatives of succinic polyisobutenylanhydride which can be obtained by the reaction of high reactivity or conventional polyisobutene having Mn = preferably 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even more especially preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride via a thermal route in an eno reaction or through chlorinated polyisobutene. Portions having hydroxyl and / or amino and / or starch and / or imido groups are, for example, carboxylic acid groups, monoamine acid amides, diamine acid amides or polyamines which, in addition to the amide function, also have free amine groups, succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboximides with diamines or polyamines which, in addition to the imide function, also have free amine groups, or diimides which are formed by the reaction diamines or polyamines with two succinic acid derivatives. In the presence of imido D (h) portions, the additional detergent additive in the context of the present invention, however, is used only up to a maximum of 100% by weight of compounds with betaine structure. Such fuel additives are common knowledge and are described, for example, in documents (1) and (2). They are preferably the alkyl or alkenyl-substituted succinic acid reaction products and more preferably the polyisobutenyl-substituted succinic acid reaction products or amine derivatives. Of particular interest in this context are reaction products with aliphatic polyamines (polyalkylenemimines) such as especially ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene hexamine and hexaethylene heptamine, which have an imide structure.
[0075] Additives comprising portions (Di) obtained through the Mannich reaction of phenols substituted with aldehydes and monoamines or polyamines are preferably reaction products of polyisobutene-phenols substituted with formaldehyde and monoamines or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. Substituted polyisobutenyl phenols can originate from high reactivity or conventional polyisobutene having Mn = 300 to 5000. Such "Mannich polyisobutene bases" are described more particularly in EP-A 831 141.
[0076] One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosage of these detergent additives is preferably 25 to 2500 ppm by weight, especially 75 to 1500 ppm by weight, in particular 150 to 1000 ppm by weight. B2) Carrier oils
[0077] Carrier oils additionally used can be of mineral or synthetic nature. Suitable mineral carrier oils are the fractions obtained in the processing of crude oil, such as clear oil or base oils having viscosities, for example, from class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanes. In the same way, a fraction which is obtained in the refining of mineral oil is useful and is known as "hydrocracking oil" (vacuum distillate cut having a boiling range of from about 360 to 500 ° C, which can be obtained from natural mineral oil which has been catalytically hydrogenated under high pressure and isomerized and also dewaxed). In the same way, mixtures of the mineral carrier oils mentioned above are suitable.
[0078] Examples of suitable synthetic carrier oils are polyolefins (poly-alpha-olefins or internal polyolefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyether amines, alkylphenol-initiated polyethers, polyether ethers initiated by alkylphenol and esters carboxylic acids of long chain alkanols.
[0079] Examples of suitable polyolefins are olefin polymers having Mn = 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or dehydrogenated).
[0080] Examples of suitable polyethers or polyether amines are preferably compounds comprising portions of polyoxy-C2 to C4-alkylene which can be obtained by the reaction of C2 to C02 alkanols, C30 to C30 alkanediools, C2 to monoalkyl amines or dialkyl amines C30, C1 to C30 alkylcyclohexanol or C1 to C30 alkyl phenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group, and, in the case of polyethers amines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described more particularly in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4 877 4,877,416. For example, the polyether amines used can be poly-C2 to C6-alkylene oxide amines or functional derivatives thereof. Typical examples of this are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia.
[0081] Examples of carboxylic esters of long chain alkanols are more particularly esters of monocarboxylic acids, dicarboxylic acids or tricarboxylic acids with long chain alkanols or polyols, as described more particularly in DE-A 38 38 918. Monocarboxylic acids, acids dicarboxylic or tricarboxylic acids used can be aliphatic or aromatic acids; particularly suitable alcohol esters or polyols esters are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellites of iso-octanol, isononanol, isodecanol and isotridecanol, for example, di (n-tridecyl or isotridecyl) phthalate.
[0082] Additional 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.
[0083] Examples of particularly suitable synthetic carrier oils are alcohol-initiated polyethers having about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and especially 15 to 30 alkylene oxide units from C3 to C6, for example example, propylene oxide, n-butylene oxide and isobutylene oxide units, or mixtures thereof, per alcohol molecule. Non-limiting examples of suitable initiator alcohols are long-chain alkanols or phenols substituted by long-chain alkyl where the long-chain alkyl radical is especially a straight or branched C6 to C18 alkyl radical. Particular examples include tridecanol and nonylphenol. Particularly preferred polyethers initiated by alcohol are the reaction products (polyetherification products) of C6 to C18 aliphatic monohydric alcohols with C3 to C6 alkylene oxides. Examples of monohydric C6 to C18 aliphatic alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and the position and constitutional isomers thereof. Alcohols can be used both in the form of pure isomers and in the form of technical grade mixtures. A particularly preferred alcohol is tridecanol. Examples of C3 to C6 alkylene oxides are propylene oxide, such as propylene 1,2-oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Particular preference among these is given to C3 to C4 alkylene oxides, i.e. propylene oxide such as propylene 1,2-oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Especially butylene oxide is used.
[0084] Additional suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.
[0085] Particular carrier oils are synthetic carrier oils, with particular preference being given to the alcohol-initiated polyethers mentioned above.
[0086] Carrier oil or a mixture of different carrier oils is added to the fuel in an amount of preferably 1 to 1000 ppm by weight, more preferably 10 to 500 ppm by weight and especially 20 to 100 ppm by weight. B3) Cold flow enhancers
[0087] Suitable cold flow enhancers are in principle all organic compounds which are capable of improving the flow performance of medium distillate fuels or diesel fuels under cold conditions. For the intended purpose, they must have sufficient oil solubility. More particularly, cold flow enhancers useful for this purpose are cold flow enhancers (medium distillate flow enhancers, MDFIs) typically used in the case of middle distillates of fossil origin, that is in the case of common mineral diesel fuels . However, it is also possible to use organic compounds that partially or predominantly have the properties of a wax-curing additive (WASA) when used in common diesel fuels. They can also act partially or predominantly as nucleators. It is also possible to use mixtures of organic compounds effective as MDFIs and / or effective as WAS As and / or effective as nucleators.
[0088] cold flow enhancer is typically selected from (Kl) copolymers of a C2 to C40 olefin with at least one additional ethylene unsaturated monomer; (K2) comb-type polymers; (K3) polyoxyalkylenes; (K4) polar nitrogen compounds; (K5) sulfo carboxylic acids or sulfonic acids or derivatives thereof; and (K6) poly (meth) acrylic esters.
[0089] It is possible to use both mixtures of different representatives from one of the particular classes (Kl) to (K6) or mixtures of representatives of different classes (Kl) to (K6).
[0090] C2 to C40 olefin monomers suitable for class (Kl) copolymers are, for example, those having 2 to 20 and especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2 carbon double bonds -carbon, especially having a carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (a-olefins) and internally. However, preference is given to α-olefins, particularly preference to α-olefins having 2 to 6 carbon atoms, for example, propene, 1-butene, 1-pentene, 1-hexene and in particular ethylene.
[0091] In class (Kl) copolymers, at least one additional ethylene unsaturated monomer is preferably selected from additional alkenyl carboxylates, (meth) acrylic esters and olefins.
[0092] When additional olefins are also copolymerized, they are preferably higher in molecular weight than the C2 to C40 olefin base monomer mentioned above. When, for example, the olefin-based monomer used is ethylene or propene, suitable additional olefins are especially CIO to C40 α-olefins. Additional olefins are in most cases only copolymerized further when monomers with carboxylic ester functions are also used.
[0093] Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C1 to C20 alkanols, especially Cl to CIO alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol, and structural isomers thereof.
Suitable alkenyl carboxylates are, for example, C2 to CM alkenyl esters, for example, vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, in which the hydrocarbon radical can be linear or branched. Among these, preference is given to vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those in which the branch is in a position for the carboxyl group, and the carbon atom is more preferably tertiary, that is, the carboxylic acid is what is called of a neocarboxylic acid. However, the hydrocarbon radical of the carboxylic acid is preferably linear.
[0095] Examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, preferably being given to vinyl esters. A particularly preferred alkenyl carboxylate is vinyl acetate; typical group (Kl) copolymers that result from it are ethylene-vinyl acetate copolymers ("EVAs"), which are some of the most frequently used.
[0096] Ethylene-vinyl acetate copolymers useful particularly advantageously and the preparation thereof are described in WO 99/29748.
Suitable class (Kl) copolymers are also those which comprise two or more different alkenyl carboxylates in copolymerized form, which differ in alkenyl function and / or in the carboxylic acid group. Likewise, copolymers are suitable which, as well as alkenyl carboxylates, comprise at least one olefin and / or at least one (meth) acrylic ester in copolymerized form.
[0098] Terpolymers of a C2 to C40 α-olefin, a C1 to C20 alkyl ester of an ethylene unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C2 to Cu alkenyl ester of a saturated monocarboxylic acid having 2 at 21 carbon atoms are also suitable as class (Kl) copolymers. Terpolymers of this type are described in WO 2005/054314. A typical terpolymer of this type is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.
[0099] At least one or the additional ethylene unsaturated monomers are copolymerized in the class (Kl) copolymers in an amount of preferably 1 to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight , based on the global copolymer. The main proportion in terms of weight of the monomer units in the class (Kl) copolymers therefore originates in general from the base olefins from C2 to C40.
[00100] Class (Kl) copolymers preferably have a numerical average molecular weight Mn of 1000 to 20,000, more preferably of 1000 to 10,000 and especially of 1000 to 8000.
[00101] Comb polymers typical of component (K2), for example, can be obtained by copolymerizing maleic anhydride or fumaric acid with another ethylene unsaturated monomer, for example, with an a-olefin or an unsaturated ester, such such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms. Additional suitable comb polymers are copolymers of esterified α-olefins and comonomers, for example, esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb-type polymers can also be polyfumarates or polyimaleates. Homopolymers and copolymers of vinyl ethers are also suitable comb-type polymers. Comb-type polymers suitable as class (K2) components are, for example, also 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). “Combined polymer mixtures are also suitable.
[00102] Polyoxyalkylene suitable as components of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ethers / ethers and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one linear alkyl group, preferably at least two linear alkyl groups, each having 10 to 30 carbon atoms and a polyoxyalkylene group having a numerical average molecular weight of up to 5000. Such polyoxyalkylene compounds are described , for example, in EP A 061 895 and also in US 4 491 455. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a numerical average molecular weight of 100 to 5000. Polyoxyalkylene monoesters and diesters are additionally suitable fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.
[00103] Polar nitrogen compounds suitable as components of class (K4) can be both ionic and non-ionic and preferably have at least one substituent, especially at least two substituents, in the form of a tertiary nitrogen atom of the general formula> NR7 in that R7 is a hydrocarbon radical from Cs to C40. Nitrogen substituents can also be categorized, that is, be in cationic form. An example of such nitrogen compounds is that of ammonium salts and / or amides that can be obtained 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 the same. The amines preferably comprise at least one linear Cs to C40 alkyl radical. Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the upper linear homologs; secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine. Amine mixtures are also suitable for this purpose, especially amine mixtures that can be obtained on an industrial scale, such as fatty amines or hydrogenated thalamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, Chapter of "Amines , aliphatic ". Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalene dicarboxylic acid, phthalic acid, isophthalic acid , terephthalic acid, and succinic acids replaced by long-chain hydrocarbon radicals.
[00104] More particularly, the class component (K4) is an oil-soluble reaction product of poly (C2 to C20 carboxylic acids) having at least one tertiary amino group with primary or secondary amines. Poly (C2 to C20 carboxylic acids) which have at least one tertiary amino group and form the basis of this reaction product preferably comprise at least 3 carboxyl groups, especially 3 to 12 and in particular 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, and are especially acetic acid units. Carboxylic acid units are suitably linked to polycarboxylic acids, commonly through one or more nitrogen and / or carbon atoms. They are preferably attached to the tertiary nitrogen atoms which, in the case of a plurality of nitrogen atoms, are connected via hydrocarbon chains.
[00105] Class component (K4) is preferably an oil-soluble reaction product based on poly (C2 to C20 carboxylic acids) that have at least one tertiary amino group and are of the general formula IIa or IIb
wherein variable A is a straight or branched chain C2 to C6 alkylene group or the portion of formula III
and variable B is an alkylene group from Cl to C19. The compounds of the general formulas 11a and 11b especially have the properties of a WASA.
[00106] Furthermore, the preferred oil-soluble reaction product of component (K4), especially that of the general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups were converted to amide groups.
[00107] C2 to Ce alkylene groups of straight or branched chain variable A are, for example, 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 and especially 2 or 3 carbon atoms.
[00108] Cl to Cl9 alkylene groups of 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 and especially 1 to 4 carbon atoms.
[00109] Primary and secondary amines as a reaction partner for polycarboxylic acids to form the component (K4) are typically monoamines, especially aliphatic monoamines. These primary and secondary amines can be selected from several amines which support hydrocarbon radicals which can optionally be linked together.
[00110] The amines related to the oil-soluble reaction products of the component (K4) are commonly secondary amines and have the general formula HN (R8) 2 in which the two variables R8 are each independently CIO to C30 alkyl radicals straight or branched, especially C14 to C24 alkyl radicals. These relatively long chain alkyl radicals are preferably straight chain or only slightly branched. In general, the secondary amines mentioned, with respect to their relatively long chain alkyl radical, are derived from naturally occurring fatty acids and from derivatives thereof. The two radicals R8 are preferably the same.
[00111] The secondary amines mentioned can be linked to polycarboxylic acids by means of amide structures or in the form of ammonium salts; it is also possible that only a portion is present in the amide structures and another portion as ammonium salts. Preferably only a few, if any, free acid groups are present. The oil-soluble reaction products of the component (K4) are preferably present completely in the form of the amide structures.
[00112] Typical examples of such components (K4) are reaction products of acetic trinitrile acid, ethylene diaminatetra acetic acid or propylene-1,2-diaminatetra acetic acid with in each case 0.5 to 1.5 mol per carboxyl group , especially 0.8 to 1.2 mol per carboxyl group, of dioleylamine, dipalmitamine, dicocoamine, distearylamine, dibehenylamine or especially di-sebum amine. A particularly preferred component (K4) is the reaction product of 1 mol of ethylenediaminetetra acetic acid and 4 moles of hydrogenated di-sebum amine.
[00113] Additional typical examples of component (K4) include the 2-N 'N, N-dialkyl ammonium salts, N'-dialkylamidobenzoates, for example, the reaction product of 1 mol of phthalic anhydride and 2 moles of di - tallow amine, the latter being hydrogenated or dehydrogenated, and the reaction product of 1 mol of an alkenylspirobislactone with 2 moles of a dialkyl amine, for example, di-tallow amine and / or tallow amine, the last two being hydrogenated or dehydrogenated.
[00114] Additional typical structure types for the class (K4) component are cyclic compounds with tertiary or condensed amino groups of primary or secondary long-chain amines with polymers containing carboxylic acid, as described in WO 93/18115.
[00115] Sulfo carboxylic acids, sulfonic acids or derivatives thereof suitable as cold flow enhancers of the class (K5) component are, for example, oil-soluble carboxamides and orthosulfobenzoic acid carboxylic esters, in which the function Sulfonic acid is present as a sulfonate with alkyl substituted ammonium cations, as described in EP-A 261 957.
[00116] Suitable (meth) acrylic polyesters as cold flow enhancers of the class (K6) component are both homopolymers and copolymers of acrylic and methacrylic esters. Preference is given to copolymers of at least two different (meth) acrylic esters that differ with respect to esterified alcohol. The copolymer optionally comprises another different olefin unsaturated monomer in copolymerized form. 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 esters of saturated C14 to Cl5 alcohols, the acid groups having been neutralized with hydrogenated talamine. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.
[00117] The cold flow enhancer or a mixture of different cold flow enhancers is added for the medium distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, more preferably 20 to 2000 ppm by weight, even more preferably from 50 to 1000 ppm by weight and especially from 100 to 700 ppm by weight, for example, from 200 to 500 ppm by weight. B4) Lubrication enhancers
[00118] Suitable lubrication enhancers 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 glyceryl monooleate. The reaction products, described in US 6 743 266 B2, of natural or synthetic oils, for example, triglycerides, and alkanolamines are also suitable as such lubrication enhancers. B5) Corrosion inhibitors
[00119] Suitable corrosion inhibitors are, for example, succinic esters, in particular with polyols, fatty acid derivatives, for example, oleic esters, oligomerized fatty acids, substituted ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation). B6) Demulsifiers
Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of phenolsulfonates and naphthalenesulfonates substituted by alkyl and the alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds such as alcohol alkoxylates , for example, alcohol ethoxylates, phenol alkoxylates, for example, tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example including in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes. B7) Disturbing agents
[00121] Suitable unsorbing agents are, for example, alkoxylated phenol-formaldehyde condensates, for example, products available under the trade name NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite). B8) Defoamers
[00122] Suitable defoamers are, for example, polyether modified polysiloxanes, for example products available under the trade name TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Coming) and RHODOSIL (Rhone Poulenc). B9) Cetane number enhancers
Suitable cetane number enhancers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide. B10) Antioxidants
[00124] Suitable antioxidants are, for example, substituted phenols, such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol, and also phenylenediamines such as N, N'-di-sec -butyl-p-phenylenediamine. B11) Metal deactivators
Suitable metal deactivators are, for example, salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine. B12) Solvents
[00126] Suitable solvents are, for example, non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, xylenes, benzine and products sold under the trade names SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), and also polar organic solvents, for example, alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents are commonly added to diesel fuel together with the aforementioned and additive additives, which they are intended to dissolve or dilute for better handling. C) Fuels
[00127] The additive of the invention is quite suitable as a fuel additive and can be used in principle in any fuels. It generates a complete series of advantageous effects in the operation of internal combustion engines with fuels. Preference is given to the use of the quantified additive of the invention in medium distilled fuels, especially diesel fuels.
[00128] The present invention therefore also provides fuels, especially medium distillate fuels, with a content of the invention's quaternized additive that is effective as an additive to achieve advantageous effects in the operation of internal combustion engines, for example, diesel engines , especially direct injection diesel engines, in particular diesel engines with common rail injection systems. This effective content (dosage) is generally 10 to 5000 ppm by weight, preferably 20 to 1500 ppm by weight, especially 25 to 1000 ppm by weight, in particular 30 to 750 ppm by weight, based on each case in the total amount of fuel.
[00129] Medium distillate fuels such as diesel fuels or heating oils are preferably mineral oil streaks which typically have a boiling range of from 100 to 400 ° C. These are commonly distilled having a 95% point up to 360 ° C or even higher. These can also be what is called "diesel with ultra low sulfur content" or "city diesel", characterized by a 95% point of, for example, no more than 345 ° C and a sulfur content of no more than 0.005% by weight or by a 95% point, for example, 285 ° C and a sulfur content of not more than 0.001% by weight. In addition to medium mineral distillate fuels or mineral diesel fuels that can be obtained through refining, those that can be obtained by coal gasification or gas liquefaction ["gas to liquid" (GTL) fuels] or by biomass liquefaction ["biomass to liquid" (BTL) fuels] are also suitable. Mixtures of the aforementioned medium distilled fuels or diesel fuels with renewable sources, such as biodiesel or bioethanol, are also suitable.
[00130] The qualities of heating oils and diesel fuels are deposited in detail, for example, in DIN 51603 and EN 590 (see also UllmaniTs Encyclopedia of Industrial Chemistry, fifth edition, Volume Al2, p. 617 ff).
[00131] In addition to its use in the aforementioned medium distillate fuels of fossil, vegetable or animal origin, which are essentially mixtures of hydrocarbon, the quatemized additive of the invention can also be used in mixtures of such medium distillates with biofuel oils (biodiesel). Such mixtures are also encompassed by the term "medium distillate fuel" in the context of the present invention. They are commercially available and commonly comprise biofuel oils in smaller quantities, typically in quantities from 1 to 30% by weight, especially from 3 to 10% by weight, based on the total amounts of the medium distillate of fossil, vegetable or animal origin. and biofuel oil.
[00132] Biofuel oils are generally based on fatty acid esters, preferably essentially on alkyl fatty acid esters derived from vegetable and / or animal oils and / or fats. Alkyl esters are typically understood to mean lower alkyl esters, especially C 1 to C 4 alkyl esters, which can be obtained by transesterification the glycerides that occur in vegetable and / or animal oils and / or fats, especially triglycerides, through lower alcohols , for example, ethanol or in particular methanol ("FAME"). Typical lower alkyl esters based on vegetable and / or animal oils and / or fats, which find use as a biofuel oil or components thereof, are, for example, sunflower methyl ester, palm oil methyl ester ("SME" "), soybean oil methyl ester (" SME ") and especially rapeseed oil methyl ester (" RME ").
[00133] Medium distillate fuels or diesel fuels are more preferably those having a low sulfur content, i.e. having a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight. weight, more particularly less than 0.005% by weight and especially less than 0.001% by weight of sulfur.
[00134] Useful gasoline fuels include all commercial gasoline fuel compositions. A typical representative that should be mentioned here is the Eurosuper base fuel of EN 228, which is quite common in the market. In addition, gasoline fuel compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention.
[00135] Quatemized additive of the invention is especially suitable as a fuel additive in combustible compositions, especially in diesel fuels, to overcome the problems highlighted in starting direct injection diesel engines, in particular those with common rail injection systems .
[00136] The invention is now illustrated in detail by the following working examples. Especially the test methods specified here below form part of the general description and are not restricted to specific working examples. Experimental: Reagents used: N-methyl-N, N-di-tallow amine: Armeen® M2HT from Akzo Nobel, CAS 61788-63-4, total amine value from 103 to 110 mg KOH / g. Heavy Naphtha Solvent from Exxon Mobil, CAS 64742-94-5. Aldrich's dimethyl oxalate, CAS 553-90-2 Aldrich's lauric acid, CAS 143-07-7 BASF 3,5,5-trimethylhexanoic acid, CAS 3302-10-1 Aldrich's methyl salicylate, CAS 119-36 -8 BASF 2-ethylhexanol, CAS 104-76-7 Aldrich's acetic acid, CAS 64-19-7 A. General test methods Engine test XUD9 test - flow restriction determination Procedure was according to standard stipulations of CEC F-23-1-01. DW10 test-determination of power loss as a result of injector deposits on the common rail diesel engine DW10-KC cleaning maintenance test
[00137] Clean maintenance test is based on the CEC test procedure F-098-08 Emission 5. This is done using the same type of engine and the same test configuration (PEUGEOT DW10) as in the CEC procedure. Special features and change:
[00138] In the tests, clean injectors were used. The cleaning time in the ultrasonic bath in water + 10% Superdecontamine (Intersciences, Brussels) at 60 ° C was 4 h. Test run times:
[00139] The test execution time was 12 h without shutdown phases. The one-hour CEC test cycle F-098-08, shown in figure 2, was performed 12 times. Performance determination:
[00140] The initial power P0, KC [kW] is calculated from the torque measured at full load 4000 / min directly after the test has started and the engine has run hot. The procedure is described in Issue 5 of the test procedure (CEC F-98-08). This is done using the same test setup and the same type of PEUGEOT DW10 engine.
[00141] Final performance (Pend, KC) is determined in the twelfth cycle in stage 12 (see the table, figure 2). Here, too, the operating point is a full load of 4000 / min. Pend, KC [kW] is calculated from the measured torque.
[00142] The power loss in the KC test is calculated as follows:
2.2. DW10 dirt-cleaning (DU-CU) The DU-CU test is based on the CEC Emission 5 test procedure F-098-08. The procedure is described in Emission 5 of the test procedure (CEC F-98-08 ). This is done using the same test setup and the same PEUGEOT DW10 type engine. The DU-CU test consists of two individual tests which are performed in succession. The first test serves to form deposits (DU), the second to remove deposits (CU). After the DU, the power loss is determined. After the end of the DU run, the engine is not operated for at least 8 hours and is cooled to room temperature. Next, CU fuel is used to start CU without uninstalling and cleaning the injectors. Deposits and loss of power ideally decline over the course of the CU test. Special features and change:
[00143] Clean injectors were installed in the engine before each DU test. The cleaning time in the ultrasound bath at 60 ° C, in water + 10% Superdecontamine (Intersciences, Brussels), was 4 h. Test run times:
[00144] The test execution time was 12 h for DU and 12 h for CU. The engine was operated in the DU and CU tests without shutdown phases.
[00145] The one-hour CEC test cycle F-098-08, shown in figure 2, was performed 12 times in each case. Performance determination:
[00146] The initial power P0, du [kW] is calculated from the torque measured at full load 4000 / min directly after the test has started and the engine has been running hot. The procedure is described in the same way in Issue 5 of the test procedure.
[00147] The final performance (Pend, du) is determined in the twelfth cycle in stage 12 (see the table above). Here, too, the operating point is a full charge of 4000 / min. Pend, du [kW] is calculated from the measured torque.
[00148] The power loss in the DU is calculated as follows:
Cleaning
[00149] The initial power P0, cu [kW] is calculated from the torque measured at a full load of 4000 / min directly after the test is started and the motor was run hot at CU. The procedure is described in the same way in Issue 5 of the test procedure.
[00150] The final performance (Pend, cu) is determined in the twelfth in stage 12 (see the table, figure 2). Here, too, the operating point is a full charge of 4000 / min. Pend, cu [kW] is calculated from the measured torque.
[00151] The power loss in the CU test is calculated as follows (negative number for the power loss in the CU test means an increase in performance)

[00152] The fuel used was Haltermann's diesel fuel (RF-06-03). To artificially induce deposit formation for injectors, 1 ppm by weight of zinc in the form of a solution of zinc didodecanoate was added to it. 3. IDID test - determination of additive action against additional injector deposits
[00153] The formation of deposits inside the injector was characterized based on the deviations in the exhaust gas temperatures from the cylinders to the cylinder outlet when the DW10 engine is cold started.
[00154] To promote the formation of deposits, 1 mg / 1 of sodium salt of an organic acid, 20 mg / 1 of dodecenyl succinic acid and 10 mg / 1 of water were added to the fuel.
[00155] The test is conducted as a cleanliness test - dirt (DU-CU).
[00156] DU-CU is based on the CEC test procedure F-098-08 Emission 5.
[00157] The DU-CU test consists of two individual tests which are performed in succession. The first test serves to form deposits (DU), the second to remove deposits (CU).
[00158] After the execution of DU, after a rest phase of at least eight hours, a cold start of the engine is conducted, followed by the idle time of 10 minutes.
[00159] Next, CU fuel is used to start CU without uninstalling and cleaning the injectors. After the CU has run 8 h, after a rest period of at least eight hours, a cold start of the engine is conducted, followed by the idle time of 10 minutes. The evaluation is carried out by comparing the temperature profiles for the individual cylinders after the cold start in the DU and CU runs.
[00160] The IDID test indicates the formation of internal deposits in the injector. The characteristics used in this test are the exhaust gas temperature of the individual cylinders. In an injector system without IDIDs, the exhaust gas temperatures of the cylinders increase evenly. In the presence of IDIDs, the exhaust gas temperatures of the individual cylinders do not increase homogeneously and deviate from each other.
[00161] The temperature sensors are beyond the cylinder head outlet on the exhaust gas manifold. Significant deviation from individual cylinder temperatures (eg> 20 ° C) indicates the presence of additional injector deposits (IDIDs).
[00162] Each of the tests (DU and CU) are conducted with an execution time of 8 h. The CEC F-098-08 hour test cycle (see figure 3) is performed 8 times in each case. In the event of deviations of individual cylinder temperatures from more than 45 ° C from the average for all 4 cylinders, the test is stopped early.
[00163] Special features and alteration: clean injectors were installed before the start of each DU test. The cleaning time in the ultrasonic bath at 60 ° C, water + 10% Superdecontamine, was 4 h. B. Preparation examples: Preparation example 1: N, N-dimethyl-N, N-di-sebum amines methyl oxalate was synthesized based on EP 2 033 945
[00164] N-Methyl-N, N-di-sebum amine (90 g) is mixed with dimethyl oxalate (90 g) and lauric acid (1.8 g). The reaction mixture is heated to 120 ° C and stirred at this temperature for 4 h. Subsequently, excess dimethyl oxalate is removed at 130 ° C under reduced pressure with the aid of a rotary evaporator. This provides 110.8 g of the product as a white wax. NMR (CDCh) confines the quaternization. Preparation example 2: N, N-dimethyl-N, N-di-sebum amines salicylate
[00165] N-Methyl-N, N-di-sebum amine (80 g) is mixed with methyl salicylate (45.4 g) and 3,5,5-trimethylhexanoic acid (0.8 g). The reaction mixture is heated to 160 ° C and stirred at this temperature for 4 h. After cooling to temperature, 124 g of the product are obtained as a white wax. NMR (CDCh) confirms the quaternization. Preparation example 3: N-methyl-N- (2-hydroxypropyl) -N, N-di-sebum amines acetate
[00166] In a 2 L autoclave, a solution of N-methyl-N, N-di-sebum amine (250 g) in 2-ethylhexanol (250 g) is mixed with acetic acid (100%, 33, 5 g). This is followed by purging N2 three times, establishing an initial pressure of approximately 1.3 bar (0.13 MPa) N2 and an increase in temperature to 50 ° C. Propylene oxide (54 g) is measured such that the temperature remains between 45 and 55 ° C. This is followed by stirring at 50 ° C for 10 h, cooling to 25 ° C, purging with N2 and emptying the reactor. The product is degassed on a rotary evaporator at 80 ° C and 20 mbar (2 KPa) for 3 h. This provides 549.4 g of the product in 2-ethylhexanol. NMR (CDCI3) confirms the quaternization. The sample is adjusted to an active ingredient content of 38% by adding Heavy Naphtha Solvent. C. Examples of use:
[00167] In the usage examples that follow, additives are used either as a pure substance (as synthesized in the preparation examples above) or in the form of an additive package.
[00168] Usage example 1: determination of the additive action in the formation of deposits in diesel engine injection nozzles a) XUD9 tests
[00169] Fuel used: RF-06-03 (reference diesel, Haltermann Products, Hamburg)
[00170] The results are summarized in Table 1. Table 1: Results of XUD9 tests
Ex. Reference Active dosage in ppm 0.1 mm needle rate flow restriction [%] # 1 according to preparation example 1 30 8.4 # 2 according to preparation example 1 15 22.4 b) DW10 test
[00171] The table shows the results of the determination of the power loss relative to 4000 rpm after 12 hours of sustained operation without interruption. The P0 value gives power after 10 minutes and the Pend value gives power at the end of the measurement:
[00172] The test results are shown in table 2. Table 2: DW10 test results

[00173] It was found that the additives of the invention according to preparation examples 1 and 2 improved the action compared to the base value. c) Action against additional injector deposits (IDID)
[00174] Fuel used: RF-06-03 (reference diesel, Haltermann Products, Hamburg)
[00175] The test results are shown in the attached figures 1 and 2.
[00176] Figure 1 shows a measurement of the exhaust gas temperatures of the cylinders in the case of using a fuel without additive; large deviations in temperature are caused by additional injector deposits.
[00177] Figure 2 shows the exhaust gas temperatures measured in the same cylinders after treatment with the additive of invention from preparation example 3, dosage of 394 mg / kg.
[00178] The measurements illustrate the action of the inventive additive for the dissolution of additional injector deposits. Exhaust gas temperature drops caused by additional injector deposits (fig. 1, cylinders 1 and 4) can be eliminated again by the additive of the invention.
[00179] Reference is made explicitly to the description of the publications cited here.

权利要求:
Claims (13)
[0001]
1. Use of a reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, in which the reaction product, obtained by of reaction of an alkyl amine that can be quaternized comprising at least one tertiary amino group that can be quaternized with a quaternizing agent that converts at least one tertiary amino group to a quaternary ammonium group, wherein the quaternizing agent is a compound of the general formula 1 R1OC (O) R2 (1) where R1 is a saturated straight or branched chain hydrocarbon radical having 1 to 4 carbon atoms and R2 is an optionally substituted monocyclic cycloalkyl or aryl radical, where the substituent is selected from from OH, NH2, NO2, C (O) ORa, and R1OC (O) -, where Ri is as defined above and R3 is H or Ri; or R2 is RiaOC (O) - where Ria is as defined above by Rq or where the quaternizing agent is a compound of the general formula 2 R1OC (O) -AC (O) ORia (2) where each of Ri and Ria is independently a saturated straight-chain or branched hydrocarbon radical having 1 to 4 carbon atoms and A is a straight-chain or one-branched or multiple branching group having 1 to 10 carbon mono-substituted or polysubstituted carbon atoms; or where the quaternizing agent comprises an epoxide of the general formula 4
[0002]
2. Use according to claim 1, characterized by the fact that the linking group A is interrupted by one or more heteroatom groups.
[0003]
Use according to claim 1 or 2, characterized in that the linking group A is an optionally monosubstituted or polysubstituted alkylene or alkenylene.
[0004]
Use according to any one of claims 1 to 3, characterized by the fact that R1 is methyl or ethyl in compounds of formula 1; and each of Ri and Ria is independently methyl or ethyl in compounds of formula 2.
[0005]
Use according to any one of claims 1 to 4, characterized by the fact that the hydrocarbon radical Ci a Cr, comprises hetero atoms in the carbon chain in compounds of formula 3.
[0006]
Use according to any one of claims 1 to 5, characterized by the fact that it is like an additive in diesel engines with common rail injection systems.
[0007]
Use according to any one of claims 1 to 6, characterized in that the quaternizing agent comprises an epoxide of the general formula 4
[0008]
Use according to claim 7, characterized in that the free protic acid is a monocarboxylic acid or a C1 to C12 dicarboxylic acid.
[0009]
Use according to any one of claims 1 to 8, characterized in that the tertiary amine that can be quaternized is a compound of the formula 3 in which at least one of the radicals Ra, Rb and Rc are the same or different and are each is a straight or branched C 1 to C 20 alkyl radical and the other radical is a C to C 4 alkyl.
[0010]
Use according to any one of claims 1 to 9, characterized by the fact that the quaternizing agent is selected from C2 to C12 alkylene oxides in combination with a monocarboxylic acid, alkyl salicylates, dialkyl phthalates and dialkyl oxalates.
[0011]
11. Use according to any one of claims 1 to 10, characterized by the fact that the fuel is selected from diesel fuels and biodiesel fuels.
[0012]
Use according to any one of claims 1 to 11, characterized by the fact that the quaternizing agent is a diakyl carboxylate.
[0013]
13. Use according to claim 12, characterized by the fact that diakyl carboxylate is a dialkyl phthalate and dialkyl oxalate.

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同族专利:

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BR112014014305A2|2017-06-13|

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KR102057028B1|2019-12-18|

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KR20140110939A|2014-09-17|

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EP2604674A1|2013-06-19|

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AU2017202811A1|2017-05-18|

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KR20190136109A|2019-12-09|

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CA2859182C|2021-03-02|

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CN104114682A|2014-10-22|

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AU2012351671A1|2014-07-10|

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-06-04| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-10-08| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-04-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-09-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP11193034.3|2011-12-12|

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EP11193034.3A|EP2604674A1|2011-12-12|2011-12-12|Use of quaternised alkylamine as additive in fuels and lubricants|

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PCT/EP2012/075244|WO2013087701A1|2011-12-12|2012-12-12|Use of quaternised alkyl amines as additives in fuels and lubricants|

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