Process for improving the injection of direct injection gasoline engines

Abstract

The present invention relates to a process for improving the injection of injectors of direct-injection gasoline engines during operation.

Description

220895W0011Process for improving the injection of direct injection gasoline enginesDescriptionThe present invention relates to a process for improving the injection of injectors of direct-injection gasoline engines during operation.Modern gasolines are unleaded in order to be compatible with catalytic convertors, and fuel injection has to be used in modern spark ignition engines, in order to achieve the required stoichiometric fuel / air mixtures. A typical fuel- injected spark ignition engine has multipoint fuel injection, in which fuel from the injectors impinges directly onto inlet valves. An unleaded base fuel in such an engine tends to give rise to inlet valve deposits. A relatively new class of spark ignition engines is the class described as direct injection spark ignition engines, also known as gasoline direct injection engines.The task of the injection pump is to precisely control the fuel dosage via the injectors, injecting it at the right moment (injection timing) and over the right period of time (injection time, duration of injection, ti). In addition, the control of the injection pump should adjust the fuel delivery depending on inter alia the engine speed and operating temperature and -conditions.To optimize the performance, torque, fuel economy, longevity, and emissions of an engine, the injection timing (i.e. the start of injection), injection duration (i.e. the injection time f), and ignition timing must be coordinated.The process of fuel combustion and its burning function in the combustion chamber, as well as the development of cylinder pressure, are determined by injection timing, injection duration, and ignition timing, which is controlled by the engine control unit (ECU), depending on the crankshaft position. The process of combustion typically reaches its maximum at around 10-20°, and the highest pressure in the cylinder (peak cylinder pressure, PCP) is reached approximately 20-30° after top dead center (ATDC).At low engine speed and load, only small amounts of fuel are required. To ensure precise dosing, the injection pressures are reduced by the engine control unit.At high engine speed and high load, large amounts of fuel must be delivered into the combustion chamber through the injector, while at the same time, the period between ignitions is shortened due to high engine speeds. Therefore, the injection pressure is increased to provide the required fuel mass. If the injection duration is chosen too long, it can lead to fuel carryover and inefficiency in combustion, resulting in increased emissions.Hence, it is desirable to strive for a short injection duration, ti.220895W0012For trouble-free running, modern direct injection spark ignition engines require automotive fuels having a complex set of properties which can only be guaranteed when use is made of appropriate gasoline additives. Such fuels usually consist of a complex mixture of chemical compounds and are characterized by physical parameters. Fuel additives are used among other things in order to avoid formation of deposits in the intake system and the intake valves of engines (keep-clean effect); on the other hand, fuel additives may be used in order to remove deposits already formed at the valves and in the intake system (clean-up effect). Special additives have been developed to reduce or minimise inlet valve deposits and also injector nozzle fouling, such additives are usually referred to as deposit control additives (DCA) and can be of different chemical nature, most often amines or quaternary ammonium salts are used. However, the presence of such deposit control additives has so far only been attributed to the cleanliness of the injectors but not to the injection properties during engine operation.M. Walter et al., "Impact of Gasoline Performance Packages on Particulate Emissions in Direct Injection Spark Ignition Engine", 2022 JSAE Annual Congress 25 to 27 May 2022, disclose a keep clean-test (KC) of an E0 gasoline fuel comprising polyisobutylene amine as additive (Fig. 2). The injection time is determined during the test and increases for the lowest allowable concentration of the polyisobutylene amine in the fuel and even for the concentration fulfilling the Top Tier requirements. For higher concentrations at best a constant injection time is observed. No reduction of injection time is observed, especially not in accordance with the TDG-F-113 test.WO 2011 / 149799 A discloses a method for providing a gain in power during the operation of an internal combustion engine by applying certain quaternary ammonium salts. Such power gain is ascribed to control of deposit formation in the engine and is explicitly described for a CEC DW10 diesel fuel injector fouling test.However, the mode of operation in a diesel engine is certainly different from that of a gasoline engine, operation conditions cannot be transferred to gasoline engines.WO 2022 / 263244 A1 describes synthesis of certain betaine-compounds and their use as fuel additives. In the context of a test for injector cleanliness a small negative change in injection time is disclosed, however, it is unclear whether the test is a dirty up- / clean up- or a keep clean-test.WO 2020 / 260062 A1 describes inter alia tertiary amines used as fuel additives. The product according to Example 2 exhibits a slight negative change in injection time.There are further disclosures, such as EP 2589647 A1 or US 2016 / 0130514 A1, in which another parameter of the engine control unit (also referred to as engine control module or engine management system) is connected with the injection time, namely the FR-value. The FR-value is a multiplier employed on the injection time and which is determined according to different operational parameters of the engine. Therefore, depending on the operational parameters and the status of the engine the FR-value may be >1 or <1 and is not identical with the injection time.220895W0013Therefore, the problem underlying the present invention is to provide a method to shorten the injection time t of injectors in direct-injection gasoline engines.The object was achieved by a process for shortening the injection time f of injectors of a direct injection spark ignition engine below the starting ignition time to, wherein the engine is operated with a gasoline fuel comprising of at least one quaternary ammonium salt as deposit control additive (DCA), wherein the starting ignition time to is the injection time determined by the engine control unit (ECU) of the direct injection spark ignition engine in order to achieve the steady state operation conditions with a constant engine speed of 2000 rpm and a constant torque of 56 Nm according to TDG F-113 for the specific gasoline fuel without any additive.Subject matter of the present invention is the observation that deposit control additives do affect the injection properties of an engine during operation.With the use of the above-mentioned deposit control additives the injection time t may be shortened compared with the starting ignition time to, which is defined as the injection time determined by the engine control unit (ECU) of the direct injection spark ignition engine in order to achieve the steady state operation conditions with a constant engine speed of 2000 rpm (+ / - 20 rpm, preferably + / - 10 rpm, more preferably + / - 5 rpm) and a constant torque of 56 Nm (+ / - 1 .5 Nm, preferably + / - 1 Nm, more preferably + / - 0.5 Nm) according to TDG F-113 (see experimental section) for the specific gasoline fuel without any additive. For the sake of clarity, the starting ignition time to is determined with a base fuel free of any additives, not only deposit control additives but also free of further gasoline fuel additives, e.g. those listed below. For the sake of clarity, the starting ignition time to is determined with a clean injector which is free of any deposits. The ECU determines the operating conditions of the injection process to provide the required fuel mass so that the engine speed of 2000 rpm and a torque of 56 Nm is reached by setting e.g. injection pressure, fuel- to-air ratio, ignition timing etc.The deposit control additive (DCA) used in this process according to the present invention is a quaternary ammonium salt.With the process according to the present invention it is possible to significantly shorten the starting injection time to, e.g. by at least 0.5%, preferably by at least 1.0 %, and even more preferably by at least 1.5%. The observed effect is more pronounced the higher the concentration of DCA in the fuel. Typically, the injection duration t is shortened to a greater extent as the concentration increases.220895W0014The effect of reducing the injection time t according to the invention is generally achieved if the engine is operated with the fuel comprising at least one DCA for a period of at least 5 hours, preferably at least 7.5 hours, more preferably at least 10 hours, and especially at least 15 hours.Independently of reducing the injection time thfouling of injectors of a direct injection spark ignition engines are cleaned up to at least 95%, preferably at least 98%, more preferably at least 99%, and especially 100% of the initial performance without the necessity to remove and externally clean the injectors from the engine.Without wishing to be bound to a theory it is believed that the observed effect is based on an absorption of the DCA on the surface of the injectors which changes the rheology of the fuel passing over the surface. For Diesel fuels, it was postulated that quaternary ammonium compounds could change the flow behaviour of the fuel by forming micelles, thereby reducing turbulence and creating a laminar flow (WO 2017 / 205772).The process according to the present invention is more pronounced at a higher concentration of deposit control additive than that which is usually present in the gasoline. This high concentration can preferably be achieved by simply metering an additive concentrate comprising the respective deposit control additive into the fuel e.g. together with a refuelling stop so that the replenishment of the fuel with the deposit control additive can simply be conducted by the driver of a vehicle or during a technical service in a car service station.It is an advantage of the present invention that the mode of action of the engine control unit resp. an injector of a direct injection spark ignition engine may be improved by the use of a deposit control engine in the gasoline used for operating the engine. As pointed out above, by shortening the injection time f it is furthermore possible to improve the efficiency of combustion and / or to reduce emissions of combustion at high engine speed and / or high load during operation of an engine.By reducing the injection time ti below the initial injection time tiO, it becomes possible to operate the engine for a longer period without cleaning measures, compared to operation with a fuel that does not contain the deposit control additive according to the invention. Such cleaning measures include operating the engine as described with a deposit control additive, and may, for example, involve a keep-clean- or clean-up-mode of operation. The advantage lies in the fact that by lowering the injection time ti below the value tiO, the engine can also be temporarily operated with a fuel that does not contain the deposit control additive according to the invention, and its performance data remain at an acceptable level until the initial value tiO is exceeded again and another cleaning measure becomes necessary.It has further been found that operating a DISI engine with gasoline fuels comprising at least one quaternary ammonium salt according to the present invention extends the time between cleaning cycles for injectors in order to restore operability of the injectors.220895W0015In the following the additive package for conducting the process according to the invention is described in more detail:The gasoline additive packages respectively gasoline compositions for use in the present invention comprise at least one quaternary ammonium salt as deposit control additive.Optionally one or more additional deposit control additives may be present, selected from the group consisting of- branched primary alkyl amines, the alkyl group having from 8 to 22 carbon atoms and a branching of at least 1 .0,- Mannich adducts, and- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, preferably- Mannich adducts, and- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, and especially- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000.The number of deposit control additives is preferably from 1 to 3, more preferably from 1 to 2, and even more preferably 1 or 2.In one embodiment of the present invention it is advantageous to use a combination of at least two, preferably two deposit control additives which are selected from different chemical classes listed above, preferably at least one quaternary ammonium compound and at least one branched primary alkyl amine, or at least one quaternary ammonium compound and at least one polyalkenemonoamine, or at least one quaternary ammonium compound and at least one Mannich adduct.The deposit control additives are described in more detail below:Branched primary alkyl aminesThe branched alkyl amines R-NH2 are primary monoamines bearing an alkyl group R having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms, the alkyl group having a branching of at least 1.0, preferably of from 1 .0 to 8.0, more preferably from 1 .5 to 7.0."Branching" in the context of the present invention means that the alkyl residue R comprises the required number of branchings. In the case of a single amine with only one branched isomer the branching of that pure compound can be easily determined on the basis of the chemical structure. In case of isomer mixtures the average branching of the220895W0016 mixture is calculated by adding up the branching of each individual isomer multiplied by the molar amount of the respective isomer in the mixture. Preferably, the branching is determined using the branching index (ISO index) (see below).The branched primary amines can be used as a mixture of amines of different molecular weight or preferably of one single molecular weight.Typical examples of such amines are the branched isomers of octyl amine, nonyl amine, decyl amine, undecyl amine, dodecyl amine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine, and heptadecyl amine, preferably nonyl amine, decyl amine, dodecyl amine, tridecyl amine, tetradecyl amine, hexadecyl amine, heptadecyl amine, eicosyl amine, docosyl amine, and mixtures thereof, more preferably nonyl amine, tridecyl amine, and heptadecyl amine, most preferably tridecyl amine and heptadecyl amine, and especially tridecyl amine.One preferred example for a branched octyl amine is 2-amino-2,4,4-trimethyl-pentane.One preferred example for a branched decyl amine is 2-propy I heptyl amine.In a preferred embodiment the branched amines according to the present invention are obtainable by oligomerization of propene, isobutene, 1 -butene or 2-butene forming a double bond-containing oligomer, followed by hydroformylation and reductive amination with ammonia. The resulting amine usually is a mixture of isomers.In another preferred embodiment the branched amines of the present invention are obtainable by amination of the corresponding branched alcohols or by reductive amination of the corresponding branched aldehydes. In this case the branching of the amines obtained is the same as that of the underlying alcohols or aldehydes, since the reaction conditions of the amination or reductive amination usually do not affect the branching of the alkyl group.In the case of the branched tridecyl amine the mixture of isomers my contain one or more of the following isomers:2,2,4,4,6,6-Hexa methyl heptyl amine, 2,4,6-tri ethyl heptyl amine, 2,3,4,5,6-penta methyl octyl amine, heptyl amines bearing 2 ethyl groups and 2 methyl groups in position 2, 4, and 6, and heptyl amines bearing 1 ethyl group and 4 methyl groups in position 2, 4, and 6.Isomer mixtures with 2,2,4,4,6,6-hexa methyl heptyl amine or 2,4,6-tri ethyl heptyl amine as main constituents are most preferred.Examples of mixtures of such branched amines are mixtures of tertiary alkyl C12- to Cu-amines (CAS No 68955-53- 3) or of C16- to C22-amines obtainable via Ritter reaction.220895W0017Amines with tertiary alkyl groups are less preferred since they exhibit a toxicity on inhalation.Hence, among the branched primary alkyl amines according to the invention those amines with the amine group bound to a primary carbon are preferred, i.e. amines bearing a group -CH2-NH2.Especially preferred is a tridecylamine isomeric mixture from BASF SE (CAS No: 86089-17-0) obtained by amination from the corresponding tridecanol isomeric mixture with a branching index of 2.2.The degree of branching is preferably described by the ISO index which indicates the average number of branches of the respective alkyl groups. Thus, for example, in the case of a Os alkyl group, the n-octyl group contributes 0, methylheptyl groups contribute 1, and dimethylhexyl groups contribute 2 to the ISO index. The lower the ISO index, the greater the linearity of the molecules in the respective group.The degree of branching is defined as the number of methyl groups in a molecule of the amine minus 1 . The average degree of branching is the statistical average of the degree of branching of the molecules of a sample. The average degree of branching can be preferably determined by1H-NMR spectroscopy as follows: a sample of the amine is firstly subject to derivatization by means of trichloroacetyl isocyanate (TAI) (literature: A. K. Bose, P. R. Srinivasan, Tetrahedron 1975, 3025; A. Postma et al., Polymer 2006, 1899). The signals of the methylene group adjacent to the amino group are at 5 = 3 to 4 ppm. All methyl, methylene and methine protons are in the range from 2.4 to 0.4 ppm. The signals < 1 ppm are assigned to the methyl groups. The average degree of branching (ISO index) can be calculated as follows from the spectrum obtained in this way:ISO index = ((A(CH3) / 3) I (A(CH2-NH2) / 2)) - 1 where A(CH3) is the signal area corresponding to the methyl protons and A(CH2-NH2) is the signal area of the methylene protons in the CH2-NH2 group. Primary amines bearing methine protons adjacent to the amino group (H2NCHR) may be analysed analogously. In the case of amines bearing a quaternary carbon atom adjacent to the amino group another distinct and assignable proton signal may be used for determining the ISO index.In the case of branched amines obtained from the corresponding branched alcohols or aldehydes by amination or reductive amination the ISO index determined according to the above-mentioned method may be used.An even more preferred1H-NMR method is handled without derivatization: The degree of branching (ISO index) of primary amines with no a-branching (H2NCH2R) is determined from their1H-NMR spectra. All NMR spectra were recorded at T = 298.2 K on a Bruker Avance III 400 spectrometer operating at 400.33 MHz for1H and 100.66 MHz for13C. The spectrometer was equipped with a 5 mm z-gradient broadband observe smartprobe. Chemical shifts are referenced to Tetramethylsilane (TMS, 5(TMS) = 0 ppm). 1 H 1D spectra were recorded using the zg pulse program with 64k data points, the relaxation delay D1 was chosen as 5 seconds, and 64 transients were recorded. For220895W0018 processing in Broker TopSpin 4.0.9 software, 32k data points were used, an exponential window function with a line broadening of 0.3 Hz was applied. Automatic baseline correction was used, phase correction was performed manually by the user. Phase sensitive HSQC spectra were recorded using the hsqcedetgpsisp2.3 pulse sequence, with 4k data points in the direct and 256 data points in the indirect dimension using 8 transients per increment. Experiments were optimized for a1JC-H coupling constant of 144 Hz. The relaxation delay D1 was set to 1.0 s. For processing, 1024 x 1024 data points were Fourier transformed, and a quadratic sine function with a sine bell shift of 2 was applied.Samples were prepared by dissolution of the pure analyte in deuterated chloroform with traces of TMS as internal reference. The samples were transferred into 5 mm NMR tubes. Deuterated solvents were purchased from Euriso- Top GmbH and used as received.For the determination of the ISO index, the integral for H2NCH2R from 5 = 2.3 - 2.95 ppm is set to a value of 2. The signals of the aliphatic methyl groups (verified by phase-sensitive HSQC spectroscopy) are integrated from 6 = 0.6 - 0.95 ppm giving the value l(Me). The degree of branching (ISO index) is calculated according to ISO index = I (Me) / 3 -1.Quaternary Ammonium SaltsIn accordance with the present invention, the deposit control additives comprise at least one quaternary ammonium salt, where a "salt" is understood here as a compound consisting of at least one cation and at least one anion, which are present separately from each other. Thus, quaternary ammonium salts do not include betaines, in which both the cationic and anionic charge centres are present within a single molecule and are linked with each other. The salts can, for example, also contain multiple, such as two, cationic charges within a molecule and the corresponding number of separately present anions; however, cations with a single positive charge and anions with a single negative charge are preferred. For the sake of simplicity "quaternary ammonium salt" and "quaternary ammonium compound" are used synonymously.The at least one quaternary nitrogen component as deposit control additive refers, in the context of the present invention, to nitrogen compounds quaternized in the presence of an acid or in an acid-free manner, preferably obtainable by addition of a compound comprising at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally at least one quaternizable amino group onto a polycarboxylic anhydride compound and subsequent quaternization.In most cases the quaternary nitrogen component is an ammonium compound, however in the context of the present document morpholinium, piperidinium, piperazinium, pyrrolidinium, imidazolinium or pyridinium cations are also encompassed by the phrase "quaternary nitrogen component".220895W0019In one embodiment the quaternary ammonium compounds are preferably of the formula+NR1R2R3R4A- in whichA- stands for an anion, preferably a carboxylate R5COO- or a carbonate R5O-COO-, andR1, R2, R3, R4, and R5independently of another are an organic residue with from 1 to 100 carbon atoms, substituted or unsubstituted, preferably unsubstituted, linear or branched alkyl, alkenyl or hydroxyalkyl residue with 1 to 100, more preferably 1 to 75, even more preferably 1 to 30, most preferably 1 to 25 and especially 1 to 20 carbon atoms,R5additionally may be substituted or unsubstituted cycloalkyl or aryl residues bearing 5 to 20, preferably 5 to 12 carbon atoms.It is also possible that the anion may be multiply charged negatively, e.g. if anions of dibasic acids are used, in this case the stoichiometric ratio of the ammonium ions to the anions corresponds to the ratio of positive and negative charges.The same is true for salts in which the cation bears more than one ammonium ion, e.g. of the substituents connect two or more ammonium ions.In the organic residues the chain of carbon atoms may be interrupted by one or more oxygen and / or sulphur atoms and / or one or more substituted or unsubstituted imino groups, and may be substituted by Ce— Ci2-aryl, C5-C12- cycloalky I or a five- or six-membered, oxygen-, nitrogen- and / or sulphur-containing heterocycle or two of them together form an unsaturated, saturated or aromatic ring which may be interrupted by one or more oxygen and / or sulphur atoms and / or one or more substituted or unsubstituted imino groups, where the radicals mentioned may each be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles.Two of the residues R1to R4may together form an unsaturated, saturated or aromatic ring, preferably a five-, six- or seven-membered ring (including the nitrogen atom of the ammonium ion).In this case the ammonium cation may be a morpholinium, piperidinium, piperazinium, pyrrolidinium, imidazolinium or pyridinium cation.In these definitions220895W00110Ci— C2o-alky I which may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, 1,1 -dimethylpropyl, 1 ,1-dimethylbutyl, 1 ,1 ,3,3-tetramethylbutyl, benzyl, 1 -phenylethyl, 2-phenylethyl, a,a-dimethylbenzyl, benzhydryl, p-tolylmethyl,1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m- ethoxybenzyl, 2-cyanoethyl, 2-cy anopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1 ,2-di-(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3- dioxolan-2-yl, 1 ,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2- butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1 ,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2- hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3- aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4- methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4- dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxy propyl, 3- phenoxypropyl, 4-phenoxybutyl, 6-phenoxy hexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4- methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxy hexyl, andC2-C2o-alkyl interrupted by one or more oxygen and / or sulphur atoms and / or one or more substituted or unsubstituted imino groups is, for example, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxaoctyl, 11 -hydroxy-3, 6,9- trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11 -hydroxy-4, 8-dioxaundecyl, 15-hydroxy-4,8, 12-trioxapentadecyl, 9-hydroxy- 5-oxanonyl, 14-hydroxy-5, 10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9- trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4, 8, 12-trioxapentadecyl, 9- methoxy-5-oxanonyl, 14-methoxy-5, 10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy- 3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11 -ethoxy-4, 8-dioxaundecyl, 15-ethoxy-4, 8, 12-trioxapentadecyl, 9-ethoxy- 5-oxanonyl or 14-ethoxy-5, 10-oxatetradecyl.If two radicals form a ring, they can together be 1 ,3-propylene, 1 ,4-butylene, 1 ,5-pentylene, 2-oxa-1,3-propylene, 1- oxa-1,3-propylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propenylene, 1-aza-1,3-propenylene, 1-Ci-C4-alkyl-1-aza-1,3- propenylene, 1 ,4-buta-1 ,3-dienylene, 1 -aza-1 ,4-buta-1 ,3-dienylene or 2-aza-1 ,4-buta-1 ,3-dienylene.The number of oxygen and / or sulphur atoms and / or imino groups is not subject to any restrictions. In general, there will be no more than 5 in the radical, preferably no more than 4 and very particularly preferably no more than 3.Furthermore, there is generally at least one carbon atom, preferably at least two carbon atoms, between any two heteroatoms.Substituted and unsubstituted imino groups can be, for example, imino, methylimino, isopropylimino, n-butylimino or tert-butylimino.220895W00111Furthermore, functional groups can be carboxy, carboxamide, hydroxy, di(Ci-C4-alkyl)amino, Ci-C4-alkyloxycarbonyl, cyano or Ci- C4-alkyloxy,Ce— Ci2-aryl which may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is, for example, phenyl, tolyl, xylyl, a-naphthyl, p-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxy phenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6- dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4- dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,C5- Ci2-cycloalkyl which may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl or a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl, a five- or six-membered, oxygen-, nitrogen- and / or sulphur-containing heterocycle is, for example, furyl, thienyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthienyl, isopropylthienyl or tert-butylthienyl andCi to C4-alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.The residues R1to R5are preferably C2-Cis-al ky I or C6-Ci2-aryl, more preferably C4-Ci6-al ky I or C6-Ci2-aryl, and even more preferably C4-Ci6-alkyl or Ce-aryl.The residues R1to R5may be saturated or unsaturated, preferably saturated.Preferred residues R1to R5do not bear any heteroatoms other than carbon or hydrogen.Preferred examples of R1to R4are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 2-propylheptyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, 1 ,1 -dimethylpropyl, 1 , 1 -dimethylbutyl, 1 ,1 ,3,3-tetramethylbutyl, benzyl, 1 -phenylethyl, 2-phenylethyl, a,a- dimethylbenzyl, benzhydryl, p-tolylmethyl or 1-(p-butylphenyl)ethyl.220895W00112In a preferred embodiment at least one of the residues R1to R4is selected from the group consisting of 2- hydroxyethyl, hydroxyprop-1 -yl, hydroxyprop-2-yl, 2-hydroxybutyl or 2-hydroxy-2-phenylethyl.In one embodiment R5is a polyolefin-homo- or copolymer, preferably a polypropylene, polybutene or polyisobutene residue, with a number-average molecular weight (Mn) of 85 to 20000, for example 113 to 10 000, or 200 to 10000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. Preferred are polypropenyl, polybutenyl and polyisobutenyl radicals, for example with a number-average molecular weight Mnof 3500 to 5000, 350 to 3000, 500 to 2500, 700 to 2500 and 800 to 1500 g / mol.Preferred examples of anions A- are the anions of acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, trimethylhexanoic acid, 2-propylheptanoic acid, isononanoic acid, versatic acids, decanoic acid, undecanoic acid, dodecanoic acid, saturated or unsaturated fatty acids with 12 to 24 carbon atoms, or mixtures thereof, salicylic acid, oxalic acid mono-Ci-C4-alkyl ester, phthalic acid mono-Ci-C4-alkyl ester, Ci2-Cioo-alkyl- and -alkenyl succinic acid, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid, and polyisobutenyl succinic acid. Further examples are methyl carbonate, ethyl carbonate, n-butyl carbonate, 2-hydroxyethyl carbonate, and 2- hydroxypropyl carbonate.In one preferred embodiment the nitrogen compounds quaternized in the presence of an acid or in an acid-free manner are obtainable by addition of a compound which comprises at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally at least one quaternizable amino group onto a polycarboxylic anhydride compound and subsequent quaternization, especially with an epoxide, e.g. styrene or propylene oxide, in the absence of free acid, as described in WO 2012 / 004300, or with a carboxylic ester, e.g. dimethyl oxalate or methyl salicylate. Suitable compounds having at least one oxygen- or nitrogen-containing group reactive with anhydride and additionally at least one quaternizable amino group are especially polyamines having at least one primary or secondary amino group and at least one tertiary amino group, especially N,N-dimethyl-1 ,3-propane diamine, N,N- dimethyl-1 ,2-ethane diamine or N,N, N'-trimethyl-1 ,2-ethane diamine. Useful polycarboxylic anhydrides are especially dicarboxylic acids such as succinic acid, having a relatively long-chain hydrocarbyl substituent, preferably having a number-average molecular weight Mnfor the hydrocarbyl substituent of 200 to 10.000, in particular of 350 to 5000. Such a quaternized nitrogen compound is, for example, the reaction product, obtained at 40°C, of polyisobutenylsuccinic anhydride, in which the polyisobutenyl radical typically has an Mnof 1000, with 3- (dimethylamino)propylamine, which constitutes a polyisobutenylsuccinic monoamide and which is subsequently quaternized with dimethyl oxalate or methyl salicylate or with styrene oxide or propylene oxide in the absence of free acid.Further quaternized nitrogen compounds suitable as compounds are described in WO 2006 / 135881 A1 , page 5, line 13 to page 12, line 14;WO 10 / 132259 A1 , page 3, line 28 to page 10, line 25;WO 2008 / 060888 A2, page 6, line 15 to page 14, line 29;220895W00113WO 2011 / 095819 A1 , page 4, line 5 to page 9, line 29;GB 2496514 A, paragraph

[0012] to paragraph

[0041] ;EP 2674471 A1 , paragraph

[0012] to paragraph

[0018] and paragraph

[0039] to paragraph

[0041] ;WO 2013 / 117616 A1 , page 3, line 34 to page 11 , line 2;WO 14 / 202425 A2, page 3, line 14 to page 5, line 9;WO 14 / 195464 A1 , page 15, line 31 to page 45, line 26 and page 75, lines 1 to 4;WO 15 / 040147 A1 , page 4, line 34 to page 5, line 18 and page 19, line 11 to page 50, line 10;WO 14 / 064151 A1 , page 5, line 14 to page 6, line 17 and page 16, line 10 to page 18, line 12;WO 2013 / 064689 A1 , page 18, line 16 to page 29, line 8;WO 2013 / 087701 A1 , page 13, line 25 to page 19, line 30,WO 13 / 000997 A1 , page 17, line 4 to page 25, line 3,WO 12 / 004300, page 5, lines 20 to 30, page 8, line 1 to page 10, line 10, and page 19, line 29 to page 28, line 3, and EP 3581638 A1 , paragraph

[0012] to paragraph

[0030] and paragraph

[0043] to paragraph

[0052] , each of which is incorporated herein by reference.In one embodiment the quaternized ammonium compound is of formulawherein in this formulaPIB stands for a polyisobutenyl residue having a number average molecular weight Mnof from 200 to 2300, preferably from 550 to 1500 and more preferably from 750 to 1300 g / mol,R stands for an Ci- to C4-al kyl or hydroxy-Ci- to C4-alkyl, preferably methyl or 2-hydroxypropyl, andA- stands for an anion, preferably carboxylate R5COO- or a carbonate R5O-COO- as defined above, more preferably acetate, salicylate or methyloxalate.In another preferred embodiment the quaternized ammonium compound is of formula220895W00114wherein in this formulaRIB stands for a polyisobutenyl residue having a number average molecular weight Mnof from 200 to 2300, preferably from 550 to 1500 and more preferably from 750 to 1300 g / mol,R stands for a hydroxy-Ci- to C^alkyl, preferably 2-hydroxypropyl.In another embodiment the quaternized compound is of formulawherein in this formulaRIB stands for a polyisobutenyl residue having a number average molecular weight Mnof from 200 to 2300, preferably from 550 to 1500 and more preferably from 750 to 1300 g / mol,R stands for an Ci- to C4-al kyl or hydroxy-Ci- to C4-alkyl, preferably methyl, andA’ stands for an anion, preferably carboxylate R5COO’ or a carbonate R5O-COO’ as defined above, more preferably salicylate or methyloxalate.In another embodiment the quaternized ammonium compound is of formula220895W00115 wherein in this formulaRIB stands for a polyisobutenyl residue having a number average molecular weight Mnof from 200 to 2300, preferably from 550 to 1500 and more preferably from 750 to 1300 g / mol,R stands for an Ci- to C4-al kyl or hydroxy-Ci- to C4-alkyl, preferably methyl or 2-hydroxypropyl,Z stands for a hydrocarbyl linker with 2 to 10 carbon units and including one or more carbon units thereof independently replaced with a bivalent moiety selected from the group consisting of -O-, -N(R')-, -C(=O)-, -C(=O)O-, or -C(=O)NR’-;R' is independently a hydrogen or a group selected from C1-6 aliphatic, phenyl, or alkylphenyl, andA- stands for an anion, preferably carboxylate R5COO- or a carbonate R5O-COO- as defined above, more preferably acetate, salicylate or methyloxalate, especially salicylate.Preferably, the amine underlying the sub-structure H2N-CH2-Z-CH2-C(CH3)2 is selected from the group consisting of 3-(2-(dimethylamino)ethoxy) propylamine and N, N-dimethyldipropylenetriamine.In another embodiment the quaternized ammonium compound is of formula owherein in this formulaRastands for Ci-C^-alkyl, preferably C9- to C -alkyl, more preferably for undecyl, tridecyl, pentadecyl or heptadecyl, Rbstands for a hydroxy -Ci- to C4-alkyl, preferably 2-hydroxypropyl or 2-hydroxybutyl, andA- stands for an anion, preferably carboxylate R5COO-, as defined above, more preferably R5COO- being a carboxylate of a fatty acid, especially A- being acetate, 2-ethylhexanoate, oleate, polyisobutenyl succinate or monoesters of polyisobutenyl succinate.In one embodiment the quaternized ammonium compound is of formulawherein in this formula220895W00116Xi for i = 1 to v and 1 to u are independently of another selected from the group consisting of -CH2-CH2-O-, -CH2- CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O- and -CH(CH3)-CH(CH3)-O-, preferably selected from the group consisting of -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2- C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O- and -CH(CH3)-CH(CH3)-O-, more preferably selected from the group consisting of -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2- CH(C2H5)-O- and -CH(C2H5)-CH2-O-, most preferably selected from the group consisting of -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-, and especially selected from the group consisting of -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-, u and v independently of another are positive integers, with the proviso that the sum (u + v) is from 2 to 50, preferably from 5 to 40, more preferably from 10 to 30, and especially from 15 to 25,R stands for an Ci- to C4-alkyl, preferably methyl, andA- stands for an anion, preferably carboxylate R5COO- or a carbonate R5O-COO- as defined above, more preferably salicylate or methyloxalate.In another preferred embodiment the quaternized ammonium compound is of formulawherein in this formulaRaand Rbindependently of another stand for Ci— C2o-alkyl or hydroxy -Ci- to C4-alkyl, preferably Rastands for C1-C20- alkyl, preferably ethyl, n-butyl, n-octyl, n-dodecyl, tetradecyl or hexadecyl, and Rbstands for hydroxy-Ci- to C4-alkyl, preferably 2-hydroxypropyl,A- stands for an anion, preferably carboxylate R5COO- or a carbonate R5O-COO- as defined above, more preferably Ci2-Cioo-alkyl- and -alkenyl succinic acid, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid, and polyisobutenyl succinic acid.Mannich adductsTypical Mannich adducts as deposit control additives are described in US 8449630 B2, preferred are Mannich adducts according to formula I of US 8449630 B2, which are incorporated by reference to the present document.220895W00117In a preferred embodiment the Mannich adducts are obtainable as described in US 8449630 B2, column 7, line 35 to column 9, line 52.Preferably the Mannich adducts are obtainable by reaction of- at least one hydrocarbyl-substituted phenol, preferably a phenol of formula V of US 8449630 B2, more preferably para hydrocarbyl-substituted phenol or para hydrocarbyl-substituted ortho-cresol, with- at least one aldehyde, preferably acetaldehyde or formaldehyde, more preferably formaldehyde, and- at least one amine according to variant 2 of US 8449630 B2, preferably selected from the group consisting of octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, cyclooctylamine, cyclodecylamine, di-n-butylamine, diisobutylamine, di-tert-butylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, di(2-ethylhexylamine), dinonylamine, didecylamine, N- methylcyclohexylamine, N-ethylcyclohexylamine, dicyclohexylamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, N, N-dipropylmethylenediamine, N, N-dipropylethylene-1, 2-diamine, N, N-dimethylpropylene- 1, 3-diamine, N, N-diethylpropylene- 1, 3-diamine, N, N-dipropylpropylene-1, 3-diamine, N, N-diethylbutylene-1, 4-diamine, N, N-dipropylbutylene-1, 4-diamine, N, N-dimethylpentylene-1 , 3-diamine, N, N- diethylpentylene- 1, 5-diamine, N, N-dipropylpentylene-1, 5-diamine, N, N-dimethylhexylene-1, 6-diamine, N, N- diethylhexylene- 1, 6-diamine, N, N-dipropylhexylene-1, 6-diamine, bis [2-(N, N-dimethylamino)ethyl] amine, bis [2- (N,N-dipropylamino)ethyl]amine, bis[3-(N, N-dimethylamino)propyl]amine, bis[3-(N, N-diethylamino)-propyl]amine, bis [3-(N,N-dipropylamino)propyl] amine, bis[4-(N, Ndimethylamino) butyl]amine, bis[4-(N, N-diethylamino) butyl]amine, bis[4-(N, N-dipropylamino)butyl]amine, bis[5-(N, N-dimethylamino)-pentyl] amine, bis[5-(N, N- diethylamino)pentyl]amine, bis[5-(N, N-dipropylamino)pentyl]amine, bis[6-(N, N-dimethylamino)-hexyl]amine, bis [6- (N,N-diethylamino)hexyl] amine, bis[6-(N, N-dipropylamino) hexyl]amine, tris[2-(N, N-dimethylamino) ethyl]amine, tris[2-(N, N-dipropylamino)ethyl]amine, tris[3-(N, N-dimethylamino)propyl] amine, tri s [3- (N,Ndiethylamino)propyl]amine, tris[3-(N, N-dipropylamino)propyl]amine, tris[4-(N, N-dimethylamino)butyl]amine, tris[4-(N, N-diethylamino)-butyl] amine, tris[4-(N, Ndipropylamino)butyl]amine, tris[5-(N, N- dimethylamino)pentyl]amine, tris[5-(N, N-diethylamino)pentyl]amine, tris[5-(N,N-dipropylamino)pentyl]amine, tris[6- (N, N-dimethylamino)hexyl]amine, tris[6-(N, N-diethylamino)-hexyl]amine, and tris[6-(N, N- dipropylamino)hexyl] amine, more preferably selected from the group consisting of dimethylamine, diethylamine, di-n-butylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N, N-dimethylpropylene- 1, 3-diamine, and N, N-diethylpropylene- 1, 3-diamine.The hydrocarbyl residue of the at least one hydrocarbyl-substituted phenol preferably has a number average molecular weight Mn of from 85 to 5000, preferably of from 113 to 2500, more preferably of from 550 to 1500, and especially from 750 to 1100.220895W00118In a preferred embodiment the hydrocarbyl residue is a polyisobutene radical of the before-mentioned molecular weight, more preferably derived from a "reactive" polyisobutene radical as defined in US 8449630 B2:"Reactive" polyisobutenes differ from low-reactivity polyisobutenes in that they have at least 50 mol%, based on the total number of polyisobutene macromolecules, of terminal double bonds. The reactive polyisobutenes preferably have at least 60 mol% and more preferably at least 80 mol%, based on the total number of polyisobutene macromolecules, of terminal double bonds. The terminal double bonds may either be vinyl double bonds [-CH=C(CH3)2] or vinylidene double bonds [-CH2-C(=CH2)-CH3]. Phenols substituted by reactive polyisobutenes and processes for preparing them are described in DE-A-19948111 , which is fully incorporated herein by way of reference. Preference is given in particular to polyisobutenes which have uniform polymer frameworks. Uniform polymer frameworks are possessed in particular by those polyisobutenes which are composed of at least 85% by weight, preferably of at least 90%by weight and more preferably of at least 95% by weight, of isobutene units.Furthermore, the reactive polyisobutenes preferably have a polydispersity of less than 3.0, in particular less than 1.9 and more preferably less than 1 .7 or less than 1 .5. Polydispersity is the quotient of the weight-average molecular weight Mw divided by the number-average molecular weight Mn.In a preferred embodiment the Mannich adduct is of formulaor of formulawhereinR10is a hydrocarbyl residue with a number average molecular weight Mn of from 85 to 5000, preferably of from 113 to 2500, more preferably of from 550 to 1500, and most preferably of from 750 to 1100, and especially is a polyisobutene radical of the before-mentioned molecular weight, more preferably derived from a "reactive"220895W00119 polyisobutene radical,R11is hydrogen, methyl, ethyl, iso-propyl, n-butyl, tert-butyl, but-2-yl, or amyl, preferably hydrogen or methyl, and more preferably methyl,R12and R13independently of another are Ci- to Ce-alkyl, preferably Ci- to C4-alkyl, more preferably are methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, even more preferably are methyl, ethyl or n-butyl, or R12and R13together the nitrogen atom form a five- or six-membered ring, preferably a pyrrolidine, piperidine or morpholine ring, and R14is bivalent alkylene residue having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably selected from the group consisting of methylene, 1 ,2-ethylene, 1 ,2-propylene, 1 ,3- propylene, 1 ,4-butylene, and 1,6-hexylene, and especially being 1 ,2-ethylene or 1 ,3-propylene.Polyalkenemono- or polyalkenepolyamines as deposit control additives are preferably based on polypropene or on high-reactivity (i.e. having predominantly terminal double bonds) or conventional (i.e. having predominantly internal double bonds) polybutene or especially polyisobutene with 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 the polyisobutene which may comprise up to 20% by weight of n-butene units by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known especially from EP-A 244 616. When polybutene or polyisobutene having predominantly internal double bonds (usually in the p and y positions) are used as starting materials in the preparation of the additives, a possible preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. The amines used here for the amination may be, for example, ammonia, monoamines or the abovementioned polyamines. Corresponding additives based on polypropene are described more particularly in WO-A 94 / 24231.Further particular additives comprising monoamino groups are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described more particularly in WO-A 97 / 03946.Further particular additives comprising monoamino groups are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described more particularly in DE-A 196 20 262.Examples of particularly useful polyalkylene radicals are polyisobutenyl radicals derived from what are called "high- reactivity" polyisobutenes which feature a high content of terminal double bonds. Terminal double bonds are alphaolefinic double bonds of the type220895W00120Polymerwhich are also referred to collectively as vinylidene double bonds. Suitable high-reactivity polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, especially greater than 80 mol% or greater than 85 mol%. Preference is given especially to polyisobutenes which have homogeneous polymer skeletons. Homogeneous polymer skeletons are possessed especially by those polyisobutenes formed from isobutene units to an extent of at least 85% by weight, preferably to an extent of at least 90% by weight and more preferably to an extent of at least 95% by weight. Such high-reactivity polyisobutenes preferably have a number-average molecular weight within the abovementioned range. In addition, the high-reactivity polyisobutenes may have a polydispersity in the range from 1.05 to 7, especially of about 1.1 to 2.5, for example of less than 1 .9 or less than 1 .5. Polydispersity is understood to mean the quotient of weight-average molecular weight Mw divided by the number-average molecular weight Mn.Particularly suitable high-reactivity polyisobutenes are, for example, the Glissopal brands from BASF SE, especially Glissopal® 1000 (Mn = 1000), Glissopal® V 33 (Mn = 550) and Glissopal® 2300 (Mn = 2300), and mixtures thereof. Other number-average molecular weights can be established in a manner known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes of particular molecular weight ranges.Due to their high proportion of vinylidene double bonds these polyisobutenes are especially reactive to undergo hydroformylation and subsequent amination, preferably with ammonia, to yield the corresponding polyisobutene amines, which represent a preferred embodiment of the present invention.Such polyisobutene amines are commercially available from BASF SE, Ludwigshafen, under the tradename KEROCOM(R) PIBA.The idealised structure of such a polyisobuteneamine isFor a number average molecular weight Mn of the underlying polyisobutene from 168 to 2300 x is from 1 to 39, for an Mn of from 224 to 1500 x is from 2 to 25, for an Mn of from 550 to 1300 x is from 8 to 21 , for an Mn of from 700 to 1300 x is from 10 to 21, and for an Mn of 950 to 1050 x is from 15 to 17.220895W00121If the underlying polyisobutene is prepared from isobutene-containing C4 hydrocarbon streams comprising monomers other than isobutene the polymeric backbone comprises other monomers in polymerised form, e.g. 1- butene and cis- and trans-2-butene, especially 1 -butene.Further to the at least one deposit control additive outlined above the gasoline fuel additive or gasoline fuel according to the present invention may optionally comprise at least one further gasoline fuel additive, selected from the group consisting of- friction modifiers- dehazers- antioxidants- metal deactivators- corrosion inhibitors,- carrier oils, and- solvents.These components are further described in more detail:Corrosion inhibitorsAs corrosion inhibitors in principle all compounds known in the art for application in fuels may be used.Suitable corrosion inhibitors are, for example, succinic esters or hemiesters, in particular with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty acids, such as dimeric fatty acid, substituted ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Afton Corporation).According to US 6043199 the latter is believed to be a reaction product of linear or branched alkyl or alkenyl substituted succinic anhydride with substituted amino-imidazolines resulting in what are believed to be linear or branched alkyl or alkenyl substituted succinimide or amine substituted succinimides.In a preferred embodiment the corrosion inhibitor is selected from the group consisting of- fatty acids or fatty acid derivatives, preferably oleic acid or its esters,- oligomerized fatty acids, preferably dimeric fatty acid, more preferably dimeric oleic acid (CAS: 61788-89-4),- alkyl or alkenyl substituted succinic acids, esters or hemiesters, and- olefin-carboxylic acid copolymers (see below).In a more preferred embodiment the corrosion inhibitor is selected from the group consisting of- oligomerized fatty acids, preferably dimeric fatty acid, more preferably dimeric oleic acid (CAS: 61788-89-4),220895W00122- alkyl or alkenyl substituted succinic acids, esters or hemiesters, and- olefin-carboxylic acid copolymers (see below). acidsFatty acids as corrosion inhibitors may be at least one saturated or unsaturated monocarboxylic acid with from 9 to 30 carbon atoms or dimers of such unsaturated monocarboxylic acids, preferably 12 to 28, more preferably 14 to 26, even more preferably 16 to 24, and especially 18 to 20 carbon atoms.The monocarboxylic acids may be saturated or unsaturated. Unsaturated carboxylic acids may bear one, two or more double bonds, preferably one or two, even more preferably one double bond.In one embodiment the monocarboxylic acid is a naturally occurring fatty acid or a mixture thereof with an even number of carbon atoms.The fatty acid as corrosion inhibitor is may be applied as a single compound or in the form of a mixture of at least 2 carboxylic acids, preferably 2 to 6 individual carboxylic acids, more preferably 2 to 5 individual carboxylic acids.In a preferred embodiment the fatty acids may be a mixture of carboxylic acids of natural origin, e.g. fatty acids which derive from vegetable and / or animal oils and / or fatsSuch fatty acids occur in vegetable and / or animal oils and / or fats, especially in the form of triglycerides from which the fatty acids are obtainable e.g. by saponification.Examples of vegetable oils are castor oil, olive oil, peanut oil, palm kernel oil, coconut oil, mustard oil, cottonseed oil, and especially sunflower oil, palm oil, soybean oil and rapeseed oil. Further examples include oils which can be obtained from wheat, jute, sesame and shea tree nut; it is additionally also possible to use arachis oil, jatropha oil and linseed oil. The extraction of these oils and the conversion thereof to the alkyl esters are known from the prior art or can be inferred therefrom.It is also possible to convert already used vegetable oils, for example used deep fat fryer oil, optionally after appropriate cleaning.Examples of animal oils and fats are fish oil, bovine tallow, porcine tallow and similar fats and oils obtained as wastes in the slaughter or utilization of farm animals or wild animals.The parent saturated or unsaturated fatty acids of said vegetable and / or animal oils and / or fats, usually has 12 to 22 carbon atoms and may bear an additional functional group such as hydroxyl groups.220895W00123Preferred are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, elaidic acid, erucic acid and / or ricinoleic acid.Preferred mixtures of fatty acids are based on vegetable and / or animal oils and / or fats are, for example, based on sunflower oil, palm oil, soybean oil, and especially rapeseed oil.It is also possible to use monocarboxylic acids which are not naturally occurring fatty acids.Preferred examples are 2-propylheptanoic acid, isononanoic acid, isotridecanoic acid, and isoheptadecanoic acid.As used herein, isononanoic acid refers to one or more branched-chain aliphatic carboxylic acids with 9 carbon atoms. Embodiments of isononanoic acid may include 7-methyloctanoic acid (e.g., CAS Nos. 693-19-6 and 26896- 18-4), 6,6-dimethylheptanoic acid (e.g., CAS No. 15898-92-7), 3,5,5-trimethylhexanoic acid (e.g., CAS No. 3302-10- 1), 3,4,5-trimethylhexanoic acid, 2,5,5-trimethylhexanoic acid, 2,2,4,4-tetramethylpentanoic acid (e.g., CAS No. 3302- 12-3) and combinations thereof. In a preferred embodiment, isononanoic acid has as its main component greater than 90% of one of 7-methyloctanoic acid, 6,6-dimethylheptanoic acid, 3,5,5-trimethylhexanoic acid, 3,4,5- trimethylhexanoic acid, 2,5,5-trimethylhexanoic acid, and 2,2,4,4-tetramethylpentanoic acid. The balance of the isononanoic acid may include other nine carbon carboxylic acid isomers and minor amounts of one or more contaminants. In a preferred embodiment, the isononanoic acid has as its main component greater than 90% of 3,5,5-trimethylhexanoic acid and even more preferably, the main component is greater than 95% 3,5,5- trimethylhexanoic acid.Dimer fatty acids are dimers of the above-mentioned unsaturated monocarboxylic acid. Such dimers usually comprise 20 to 60 carbon atoms, preferably 24 to 44, more preferably 28 to 40, and especially 32 to 38 carbon atoms.The dimer may comprise trimers or higher oligomers of unsaturated monocarboxylic acid in minor amounts.Dimerisation respectively oligomerisation usually takes place via Diels-Alder reaction so that the dimers typically comprise at least one substituted cyclohexene substructure. It is also possible that oligomerisation takes place via Alder ene-reaction or radical oligomerisation.The at least one carboxylic acid is applied in the form of the free acid, i.e. COOH groups are present. To a minor extent, some of the carboxylic functions may be present in salt form, e.g. as alkali or alkaline metal salts salts or as ammonium or substituted ammonium salts, depending on the pH value of the liquid phase. Preferably at least 50 % of all carboxylic acid groups are available in the form of the free acid as COOH-groups, more preferably at least 66 %, very preferably at least 75 %, even more preferably at least 85 %, and especially at least 95%.220895W00124Alkyl or alkenyl substituted succinic acids, esters or hemiestersThe succinic acids, esters or hemiesters are preferably substituted with Cs- to Cioo-alkyl or -alkenyl radicals.In a preferred embodiment the succinic acids or hemiesters follow formulawhereinR20is a Cs- to C 100-al ky I or Cs- to C 100-alkeny I group, preferably Cs- to Cioo-alkenyl, more preferably C12- to Cgo-alkenyl, and even more preferably C16- to Cso-alkenyl group, andR21is hydrogen or Ci- to C2o-alkyl or C2- to Ci-hydroxyalkyl, preferably hydrogen.The underlying succinic acid anhydrides are obtainable by thermal ene reaction of Cs- to Cioo-alkenes, preferably oligomers or polymers of propene, 1 -butene or isobutene, with maleic anhydride. The above-mentioned corrosion inhibitors are obtainable from such anhydrides by hydrolysis or reaction with the appropriate alcohol.Olefin-carboxylic acid copolymersThe olefin-carboxylic acid copolymer (A) is a copolymer obtainable by- in a first reaction step (I) copolymerizing(Aa) at least one ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid,(Ab) at least one a-olefin having from at least 12 up to and including 30 carbon atoms,(Ac) optionally at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and is different than (Ab) and220895W00125(Ad) optionally one or more further copolymerizable monomers other than monomers (Aa), (Ab) and (Ac), selected from the group consisting of(Ada) vinyl esters,(Adb) vinyl ethers,(Adc) (meth)acrylic esters of alcohols having at least 5 carbon atoms,(Add) allyl alcohols or ethers thereof,(Ade) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-vinyllactams, (Adf) ethylenically unsaturated aromatics, (Adg) a,p-ethylenically unsaturated nitriles, (Adh) (meth)acrylamides and(Adi) allylamines, followed by- in a second optional reaction step (II) partly or fully hydrolyzing and / or saponifying anhydride or carboxylic ester functionalities present in the copolymer obtained from (I), the second reaction step being run at least when the copolymer obtained from reaction step (I) does not comprise any free carboxylic functionalities.Description of the copolymer (A)The monomer (Aa) is at least one, preferably one to three, more preferably one or two and most preferably exactly one ethylenically unsaturated, preferably a,p-ethylenically unsaturated, mono- or dicarboxylic acid(s) or derivatives thereof, preferably a dicarboxylic acid or derivatives thereof.Derivatives are understood to mean- the corresponding anhydrides in monomeric or else polymeric form,- mono- or dialkyl esters, preferably mono- or di-Ci-C4-alkyl esters, more preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, and- mixed esters, preferably mixed esters having different C1-C4 alkyl components, more preferably mixed methyl ethyl esters.Preferably, the derivatives are anhydrides in monomeric form or di-Ci-C4-alkyl esters, more preferably anhydrides in monomeric form.In the context of this document, Ci-C4-alkyl is understood to mean methyl, ethyl, / so-propyl, n-propyl, n-butyl, / so- butyl, sec-butyl and tert-butyl, preferably methyl and ethyl, more preferably methyl.220895W00126Examples of a, p-ethy lenical ly unsaturated mono- or dicarboxylic acids are those mono- or dicarboxylic acids or derivatives thereof in which the carboxyl group or, in the case of dicarboxylic acids, at least one carboxyl group, preferably both carboxyl groups, is / are conjugated to the ethylenically unsaturated double bond.Examples of ethylenically unsaturated mono- or dicarboxylic acids that are not a, p-ethy lenically unsaturated are cis- 5-norbornene-endo-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1 ,2,3,6-tetrahydrophthalic anhydride and cis-4- cyclohexene-1 , 2-dicarboxy I ic anhydride.Examples of a, p-ethy lenically unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, cratonic acid and ethylacrylic acid, preferably acrylic acid and methacrylic acid, referred to in this document as (meth)acrylic acid for short, and more preferably acrylic acid.Particularly preferred derivatives of a, p-ethy lenically unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate.Examples of dicarboxylic acids are maleic acid, fumaric acid, itaconic acid (2-methylenebutanedioic acid), citraconic acid (2-methylmaleic acid), glutaconic acid (pent-2-ene-1 ,5-dicarboxylic acid), 2,3-dimethylmaleic acid, 2- methylfumaric acid, 2,3-dimethylfumaric acid, methylenemalonic acid and tetrahydrophthalic acid, preferably maleic acid and fumaric acid and more preferably maleic acid and derivatives thereof.More particularly, monomer (Aa) is maleic anhydride.Monomer (Ab) is at least one, preferably one to four, more preferably one to three, even more preferably one or two and most preferably exactly one o-olefin(s) having from at least 12 up to and including 30 carbon atoms. The a- olefins (Ab) preferably have at least 14, more preferably at least 16 and most preferably at least 18 carbon atoms. Preferably, the o-olefins (Ab) have up to and including 28, more preferably up to and including 26 and most preferably up to and including 24 carbon atoms.Preferably, the o-olefins may be one or more linear or branched, preferably linear, 1 -alkene.Examples of these are 1 -dodecene, 1 -tridecene, 1 -tetradecene, 1 -pentadecene, 1 -hexadecene, 1 -heptadecene, 1- octadecene, 1-nonodecene, 1-eicosene, 1-docosene, 1 -tetracosene, 1 -hexacosene, preference being given to 1- octadecene, 1-eicosene, 1-docosene and 1 -tetracosene, and mixtures thereof.Further examples of o-olefin (Ab) are those olefins which are oligomers or polymers of C2 to C12 olefins, preferably of C3 to C10 olefins, more preferably of C4 to Ce olefins. Examples thereof are ethene, propene, 1 -butene, 2-butene, isobutene, pentene isomers and hexene isomers, preference being given to ethene, propene, 1 -butene, 2-butene and isobutene.220895W00127Named examples of a-olefins (Ab) include oligomers and polymers of propene, 1 -butene, 2-butene, isobutene, and mixtures thereof, particularly oligomers and polymers of propene or isobutene or of mixtures of 1 -butene and 2- butene. Among the oligomers, preference is given to the trimers, tetramers, pentamers and hexamers, and mixtures thereof.In addition to the olefin (Ab), it is optionally possible to incorporate at least one, preferably one to four, more preferably one to three, even more preferably one or two and especially exactly one further aliphatic or cycloaliphatic olefin(s) (Ac) which has / have at least 4 carbon atoms and is / are different than (Ab) by polymerization into the inventive copolymer.The olefins (Ac) may be olefins having a terminal (o-)double bond or those having a non-terminal double bond, preferably having an o-double bond. The olefin (Ac) preferably comprises olefins having 4 to fewer than 12 or more than 30 carbon atoms. If the olefin (Ac) is an olefin having 12 to 30 carbon atoms, this olefin (Ac) does not have an a- double bond.Examples of aliphatic olefins (Ac) are 1 -butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers and mixtures thereof.Examples of cycloaliphatic olefins (Ac) are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, a- or p-pinene and mixtures thereof, limonene and norbornene.Further examples of olefins (Ac) are polymers having more than 30 carbon atoms of propene, 1 -butene, 2-butene or isobutene or of olefin mixtures comprising the latter, preferably of isobutene or of olefin mixtures comprising the latter, more preferably having a mean molecular weight Mwin the range from 500 to 5000 g / mol, preferably 650 to 3000 and more preferably 800 to 1500 g / mol.Preferably, the oligomers or polymers comprising isobutene in copolymerized form have a high content of terminal ethylenic double bonds (o-double bonds), for example at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol% and most preferably at least 80 mol%.For the preparation of such oligomers or polymers comprising isobutene in copolymerized form, suitable isobutene sources are either pure isobutene or isobutene-containing C4 hydrocarbon streams, for example C4 raffinates, especially "raffinate 1", C4 cuts from isobutane dehydrogenation, C4 cuts from steamcrackers and from FCC crackers (fluid catalyzed cracking), provided that they have substantially been freed of 1 ,3-butadiene present therein. A C4 hydrocarbon stream from an FCC refinery unit is also known as a "b / b" stream. Further suitable isobutene- containing C4 hydrocarbon streams are, for example, the product stream of a propylene-isobutane cooxidation or the product stream from a metathesis unit, which are generally used after customary purification and / or concentration. Suitable C4 hydrocarbon streams comprise generally less than 500 ppm, preferably less than 200 ppm, of butadiene.220895W00128The presence of 1-butene and of cis- and trans-2-butene is substantially uncritical. Typically, the isobutene concentration in said C4 hydrocarbon streams is in the range from 40% to 60% by weight. For instance, raffinate 1 generally consists essentially of 30% to 50% by weight of isobutene, 10% to 50% by weight of 1-butene, 10% to 40% by weight of cis- and trans-2-butene and 2% to 35% by weight of butanes; in the polymerization process the unbranched butenes in the raffinate 1 are generally virtually inert, and only the isobutene is polymerized.In a preferred embodiment, the monomer source used for polymerization is a technical C4 hydrocarbon stream having an isobutene content of 1% to 100% by weight, especially of 1% to 99% by weight, in particular of 1% to 90% by weight, more preferably of 30% to 60% by weight, especially a raffinate 1 stream, a b / b stream from an FCC refinery unit, a product stream from a propylene-isobutane cooxidation or a product stream from a metathesis unit.Especially when a raffinate 1 stream is used as isobutene source, the use of water as the sole initiator or as further initiator has been found to be useful, particularly when polymerization is effected at temperatures of -20°C to +30°C, especially of 0°C to +20°C. At temperatures of -20°C to +30°C, especially of 0°C to +20°C, however, it is possible to dispense with the use of an initiator when using a raffinate 1 stream as isobutene source.Said isobutene-containing monomer mixture may comprise small amounts of contaminants such as water, carboxylic acids or mineral acids without causing any critical yield or selectivity losses. It is appropriate to the purpose to avoid accumulation of these impurities by removing such harmful substances from the isobutene-containing monomer mixture, for example, by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.It is also possible, albeit less preferable, to convert monomer mixtures of isobutene or of the isobutene-containing hydrocarbon mixture with olefinically unsaturated monomers copolymerizable with isobutene. If monomer mixtures of isobutene with suitable comonomers are to be copolymerized, the monomer mixture comprises preferably at least 5% by weight, more preferably at least 10% by weight and especially at least 20% by weight of isobutene, and preferably at most 95% by weight, more preferably at most 90% by weight and especially at most 80% by weight of comonomers.In a preferred embodiment, the mixture of the olefins (Ab) and optionally (Ac), averaged to their molar amounts, have at least 12 carbon atoms, preferably at least 14, more preferably at least 16 and most preferably at least 17 carbon atoms.For example, a 2:3 mixture of docosene and tetradecene has an averaged value for the carbon atoms of 0.4 * 22 + 0.6 x 14 = 17.2.The upper limit is less relevant and is generally not more than 60 carbon atoms, preferably not more than 55, more preferably not more than 50, even more preferably not more than 45 and especially not more than 40 carbon atoms.220895W00129The optional monomer (Ad) is at least one monomer, preferably one to three, more preferably one or two and most preferably exactly one monomer(s) selected from the group consisting of (Ada) vinyl esters, (Adb) vinyl ethers,(Adc) (meth)acrylic esters of alcohols having at least 5 carbon atoms,(Add) allyl alcohols or ethers thereof,(Ade) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-vinyllactams, (Adf) ethy lenically unsaturated aromatics and(Adg) a,p-ethylenically unsaturated nitriles,(Adh) (meth)acrylamides and(Adi) allylamines.Examples of vinyl esters (Ada) are vinyl esters of C2- to Ci2-carboxylic acids, preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl decanoate, and vinyl esters of Versatic Acids 5 to 10, preferably vinyl esters of 2,2-dimethylpropionic acid (pivalic acid, Versatic Acid 5), 2,2-dimethylbutyric acid (neohexanoic acid, Versatic Acid 6), 2,2-dimethylpentanoic acid (neoheptanoic acid, Versatic Acid 7), 2,2-dimethylhexanoic acid (neooctanoic acid, Versatic Acid 8), 2,2- dimethylheptanoic acid (neononanoic acid, Versatic Acid 9) or 2,2-di methy loctanoic acid (neodecanoic acid, Versatic Acid 10).Examples of vinyl ethers (Adb) are vinyl ethers of Ci- to Ci2-alkanols, preferably vinyl ethers of methanol, ethanol, / so-propanol, n-propanol, n-butanol, / so-butanol, sec-butanol, ferf-butanol, n-hexanol, n-heptanol, n-octanol, n- decanol, n-dodecanol (lauryl alcohol) or 2-ethy I hexanol.Preferred (meth)acrylic esters (Adc) are (meth)acrylic esters of C5- to C 12-alkanols, preferably of n-pentanol, n- hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol or 2-propylheptanol. Particular preference is given to pentyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate.Examples of monomers (Add) are allyl alcohols and allyl ethers of C2- to Ci2-alkanols, preferably allyl ethers of methanol, ethanol, / so-propanol, n-propanol, n-butanol, / so-butanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.Examples of vinyl compounds (Ade) of heterocycles comprising at least one nitrogen atom are N-vinylpyridine, N- vinylimidazole and N-vinylmorpholine.Preferred compounds (Ade) are N-vinylamides or N-vinyllactams.220895W00130Examples of N-vinylamides or N-vinyllactams (Ade) are N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and N-vinylcaprolactam.Examples of ethylenically unsaturated aromatics (Adf) are styrene and o-methylstyrene.Examples of a,p-ethylenically unsaturated nitriles (Adg) are acrylonitrile and methacrylonitrile.Examples of (meth)acrylamides (Adh) are acrylamide and methacrylamide.Examples of allylamines (Adi) are allylamine, dialkylallylamine and trialkylallylammonium halides.Preferred monomers (Ad) are (Ada), (Adb), (Adc), (Ade) and / or (Adf), more preferably (Ada), (Adb) and / or (Adc), even more preferably (Ada) and / or (Adc) and especially (Adc).The incorporation ratio of the monomers (Aa) and (Ab) and optionally (Ac) and optionally (Ad) in the polymer obtained from reaction step (I) is generally as follows:The molar ratio of (Aa) / ((Ab) and (Ac)) (in total) is generally from 10:1 to 1 :10, preferably 8:1 to 1 :8, more preferably 5:1 to 1 :5, even more preferably 3:1 to 1 :3, particularly 2:1 to 1 :2 and especially 1.5:1 to 1 :1.5. In the preferred particular case of maleic anhydride as monomer (Aa), the molar incorporation ratio of maleic anhydride to monomers ((Ab) and (Ac)) (in total) is about 1 :1.The molar ratio of obligatory monomer (Ab) to monomer (Ac), if present, is generally of 1:0.05 to 10, preferably of 1 :0.1 to 6, more preferably of 1 :0.2 to 4, even more preferably of 1 :0.3 to 2.5 and especially 1 :0.5 to 1 .5.In a preferred embodiment, no optional monomer (Ac) is present in addition to monomer (Ab).The proportion of one or more of the monomers (Ad), if present, based on the amount of the monomers (Aa), (Ab) and optionally (Ac) (in total) is generally 5 to 200 mol%, preferably 10 to 150 mol%, more preferably 15 to 100 mol%, even more preferably 20 to 50 mol% and especially 0 to 25 mol%.In a preferred embodiment, no optional monomer (Ad) is present.In a second reaction step (II), the anhydride or carboxylic ester functionalities present in the copolymer obtained from (I) are partly or fully hydrolyzed and / or saponified.220895W00131Reaction step (II) is obligatory in case the copolymer obtained from reaction step (I) does not comprise free carboxylic acid groups.Hydrolization of anhydride groups is preferred over saponification of ester groups.Preferably, 10% to 100% of the anhydride or carboxylic ester functionalities present are hydrolyzed and / or saponified, preferably at least 20%, more preferably at least 30%, even more preferably at least 50% and particularly at least 75% and especially at least 85%.For a hydrolysis, based on the anhydride functionalities present, the amount of water that corresponds to the desired hydrolysis level is added and the copolymer obtained from (I) is heated in the presence of the added water. In general, a temperature of preferably 20 to 150°C is sufficient for the purpose, preferably 60 to 100°C. If required, the reaction can be conducted under pressure in order to prevent the escape of water. Under these reaction conditions, in general, the anhydride functionalities in the copolymer are converted selectively, whereas any carboxylic ester functionalities present in the copolymer react at least only to a minor degree, if at all.For a saponification, the copolymer is reacted with an amount of a strong base corresponding to the desired saponification level in the presence of water.Strong bases used may preferably be hydroxides, oxides, carbonates or hydrogencarbonates of alkali metals or alkaline earth metals.The copolymer obtained from (I) is then heated in the presence of the added water and the strong base. In general, a temperature of preferably 20 to 130°C is sufficient for the purpose, preferably 50 to 110°C. If required, the reaction can be conducted under pressure.It is also possible to hydrolyze the carboxylic ester functionalities with water in the presence of an acid. Acids used are preferably mineral acids, carboxylic acids, sulfonic acids or phosphorus acids having a pKa of not more than 5, more preferably not more than 4.Examples are acetic acid, formic acid, oxalic acid, salicylic acid, substituted succinic acids, aromatically substituted or unsubstituted benzenesulfonic acids, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; the use of acidic ion exchange resins is also conceivable.In a preferred embodiment for anhydrides, especially maleic anhydride being monomers (Aa), such anhydride moieties are partly or fully, especially fully hydrolysed while potentially existing ester groups in the copolymer remain intact. In this case no saponification in step (II) takes place.220895W00132The copolymer obtained from (I) is then heated in the presence of the added water and the acid. In general, a temperature of preferably 40 to 200°C is sufficient for the purpose, preferably 80 to 150°C. If required, the reaction can be conducted under pressure.Should the copolymers obtained from step (II) still comprise residues of acid anions, it may be preferable to remove these acid anions from the copolymer with the aid of an ion exchanger and preferably exchange them for hydroxide ions or carboxylate ions, more preferably hydroxide ions. This is the case especially when the acid anions present in the copolymer are halides or contain sulfur or nitrogen.The copolymer obtained from reaction step (II) generally has a weight-average molecular weight Mw of 0.5 to 20 kDa, preferably 0.6 to 15, more preferably 0.7 to 7, even more preferably 1 to 7 and especially 1.5 to 4 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).The number-average molecular weight Mn is usually from 0.5 to 10 kDa, preferably 0.6 to 5, more preferably 0.7 to 4, even more preferably 0.8 to 3 and especially 1 to 2 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).The polydispersity is generally from 1 to 10, preferably from 1.1 to 8, more preferably from 1.2 to 7, even more preferably from 1 .3 to 5 and especially from 1 .5 to 3.The content of acid groups in the copolymer is preferably from 1 to 8 mmol / g of copolymer, more preferably from 2 to 7.5, even more preferably from 3 to 7 mmol / g of copolymer.In a preferred embodiment, the copolymers comprise a high proportion of adjacent carboxylic acid groups, which is determined by a measurement of adjacency. For this purpose, a sample of the copolymer is heat-treated between two Teflon films at a temperature of 290°C for a period of 30 minutes and an FTIR spectrum is recorded at a bubble- free site. The IR spectrum of Teflon is subtracted from the spectra obtained, the layer thickness is determined and the content of cyclic anhydride is determined.In a preferred embodiment, the adjacency is at least 10%, preferably at least 15%, more preferably at least 20%, even more preferably at least 25% and especially at least 30%.The olefin-carboxylic acid copolymer (A) is applied in the form of the free acid, i.e. COOH groups are present, or in the form of the anhydride which may be an intramolecular anhydride or an intermolecular anhydride linking two dicarboxylic acid molecules together, preferably in the form of a free acid. To a minor extent, some of the carboxylic functions may be present in salt form, e.g. as alkali or alkaline metal salts salts or as ammonium or substituted ammonium salts, depending on the pH value of the liquid phase. Preferably at least 50 % of all carboxylic acid groups are available in the form of the free acid as COOH-groups, more preferably at least 66 %, very preferably at220895W00133 least 75 %, even more preferably at least 85 %, and especially at least 95%. A single olefin-carboxylic acid copolymer (A) or a mixture of different olefin-carboxylic acid copolymers (A) may be used.Carrier oilsCarrier oils additionally used may be of mineral or synthetic nature. Suitable mineral carrier oils are fractions obtained in crude oil processing, such as brightstock or base oils having viscosities, for example, from the SN 500 - 2000 class; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Likewise useful is a fraction which is obtained in the refining of mineral oil and is known as "hydrocrack oil" (vacuum distillate cut having a boiling range of from about 360 to 500°C, obtainable from natural mineral oil which has been catalytically hydrogenated under high pressure and isomerized and also deparaffinized). Likewise suitable are mixtures of the abovementioned mineral carrier oils.Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or poly internalolefi ns), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic esters of long-chain alkanols.Examples of suitable polyolefins are olefin polymers having Mn= 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or unhydrogenated).Examples of suitable polyethers or polyetheramines are preferably compounds comprising polyoxy-C2- to Chalky lene moieties obtainable by reacting C2- to Ceo-alkanols, Ce- to Cao-alkanediols, mono- or di-C2- to Cao-alkylamines, Ci- to Cao-alkylcyclohexanols or Ci- to C 30-al ky Iphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group, and, in the case of the polyetheramines, 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. For example, the polyetheramines used may be poly-C2- to Ce-alkylene oxide amines or functional derivatives thereof. Typical examples thereof are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia.Examples of carboxylic esters of long-chain alkanols are more particularly esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described more particularly in DE-A 38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids; particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, for example di(n- or isotridecyl) phthalate.220895W00134Further suitable carrier oil systems are described, for example, in DE-A 3826 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548617.Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and especially 15 to 30 C3- to Ce-alkylene oxide units, for example propylene oxide, n-butylene oxide and isobutylene oxide units, or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or phenols substituted by long-chain alkyl in which the long-chain alkyl radical is especially a straight-chain or branched Ce- to Cis-alkyl radical. Particular examples include tridecanol, heptadecanol and nonylphenol. Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic Ce- to G -alcohols with C3- to Ce-alkylene oxides. Examples of monohydric aliphatic Ce-Cis-alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3- propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol and the constitutional and positional isomers thereof. The alcohols can be used either in the form of the pure isomers or in the form of technical grade mixtures. A particularly preferred alcohol is tridecanol. Examples of C3- to Ce-alkylene oxides are propylene oxide, such as 1 ,2-propylene oxide, butylene oxide, such as 1 ,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Particular preference among these is given to C3- to C4-alkylene oxides, i.e. propylene oxide such as 1 ,2-propylene oxide and butylene oxide such as 1 ,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Especially butylene oxide is used.Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.Particular carrier oils are synthetic carrier oils, particular preference being given to the above-described alcohol- started polyethers and polyether amines.Other additivesTypical other additives in the additive packages or fuels according to the invention may be friction modifier, dehazers, antioxidants, metal deactivators, and solvents for the packages.Friction modifierSuitable friction modifiers are based typically on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described, for example, in WO 98 / 004656, and glyceryl monooleate. The reaction products, described in US 6743266 B2, of natural or synthetic oils, for example triglycerides, and alkanolamines are also suitable as such friction modifier.Preferred lubricity improvers are described in WO 15 / 059063 and WO 10 / 005720. Furthermore, hydroxyl groupsubstituted tertiary amines as disclosed in WO 2014 / 23853 are preferred as friction modifiers.220895W00135Preferably the friction modifier is selected from the group consisting of-- Propoxylated and / or butoxylated reaction product of (a) one or more fatty acids and (b) a dialkanolamine and-- one or more fatty acids.Propoxylated and / or butoxylated reaction product of (a) one or more fatty acids and (b) a dialkanolamineSuch a friction modifier is a propoxylated and / or butoxylated reaction product of (a) one or more fatty acids, one or more fatty acid ester, or mixtures thereof and (b) a dialkanolamine, such as diethanolamine.More particularly, compound comprises a propoxylated and / or butoxylated amide having a formula (I) and an ester compound of formula I (a):(I) R7-C(=O)-N-[-CHRcCHRd-O-(-CHR8-CHR9-O)nH] [-CHRcCHRd-O-(CHR8-CHR9-O)m-H|(la) R7-C(=O)-O-CHRcCHRd-N-[-CHRcCHRdO-(CHR8CHR9-O)q-H] [-(CHR8CHR9-O)P-H] wherein R7is a linear or branched, saturated or unsaturated, C7-C23, aliphatic hydrocarbon radical, optionally containing at least one hydroxyl group; both Rcand Rdare hydrogen or one of Rcand Rdis hydrogen and the other of Rcand Rdis methyl;-CHR8-CHR9-O independently is -CH2-CH(CH3)-O, -CH2-CH(C2H5)-O, -CH(CH3)-CH2-O or -CH(C2H5)-CH2-O n+m is 0.5 to 5, wherein n and m can be the same or different and one of n and m can be 0; and p + q is 0 to 5, wherein p and q can be the same or different and q alone or both p and q can be 0.In preferred embodiments, p + q is 0 to 3, more preferably p is 0 to 3 and q is 0, and most preferably p is 1 to 3 and q is 0.In some embodiments, the amide is propoxylated, i.e. one of R2and R3is hydrogen and the other is methyl. In other embodiments, the amide is butoxylated, i.e. one of R2and R3is hydrogen and the other is ethyl. In still further embodiments, the amide is propoxylated and butoxylated. In preferred embodiments, n+m is 1 to 5, and more preferably 1 to 3.220895W00136Another aspect of the present invention is to provide a method of improving the fuel economy of an internal combustion engine comprising adding an amide of formula (I) and ester of formula (la) to a hydrocarbon fuel, and using the resulting fuel in an internal combustion engine.More particularly, the present propoxy lated / butoxy lated amides and esters of structural formula (I) and (la) are prepared by first reacting at least one fatty acid and / or at least one fatty acid ester with a dialkanolamine to form a dialkanolamide and ester. The dialkanolamide and -ester then are propoxlated and / or butoxylated with one to five moles of propylene oxide and / or butylene oxide. The dialkanolamide and -ester are free of alkoxylation using ethylene oxide. The major product is the amide of formula (I), with the ester of formula (la) being present in an amount of up to 30%, and more particularly about 0.1% to about 30%, by total weight of amide (I) and ester (la).More particularly, the fatty acid and / or fatty acid ester used in the reaction to form an amide contains 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 18 carbon atoms. The fatty acid and / or fatty acid ester therefore can be, but not limited to, lauric acid, myristic acid, palmitic acid, stearic acid, octanoic acid, pelargonic acid, behenic acid, cerotic acid, monotanic acid, lignoceric acid, doeglic acid, erucic acid, linoleic acid, isanic acid, stearodonic acid, arachidonic acid, chypanudoic acid, ricinoleic acid, capric acid, decanoic acid, isostearic acid, gadoleic acid, myristoleic acid, palmitoleic acid, linderic acid, oleic acid, petroselenic acid, esters thereof, and mixtures thereof.The fatty acid / fatty acid ester also can be derived from a vegetable oil or an animal oil, for example, but not limited to, coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, castor oil, peanut oil, jojoba oil, soy oil, sunflower seed oil, walnut oil, sesame seed oil, rapeseed oil, rape oil, beef tallow, lard, whale blubber, seal oil, dolphin oil, cod liver oil, corn oil, tall oil, cottonseed oil, and mixtures thereof. The vegetable oils contain a mixture of fatty acids. For example, coconut oil typically contains the following fatty acids: caprylic (8%), capric (7%), lauric (48%). myristic (17.5%), palmitic (8.2%), stearic (2%), oleic (6%), and linoleic (2.5%).The fatty acid component of the amide of formula (II) and ester of formula (Ila) also can be derived from fatty acid esters, such as, for example, glyceryl trilaurate, glyceryl tristearate, glyceryl tripalmitate, glyceryl dilaurate, glyceryl monostearate, ethylene glycol dilaurate, pentaerythritol tetrastearate, pentaerythritol trilaurate, sorbitol monopalmitate, sorbitol pentastearate, propylene glycol monostearate, and mixtures thereof.The fatty acid component comprises one or more fatty acid per se, one or more fatty acid methyl ester, one or more fatty acid ethyl ester, one or more vegetable oil. one or more animal oil, and mixtures thereof. The amide resulting from the reaction can contain byproducts, such as glycerin, ethylene glycol, sorbitol, and other polyhydroxy compounds. The water, methanol, and ethanol by-products from these embodiments are readily removed from the reaction, if desired, to substantially reduce the amount of unwanted by-products. The byproduct polyhydroxy compounds do not adversely affect the final propoxylated / butoxylated amide (I) and typically are allowed to remain in the reaction mixture.220895W00137A preferred fatty acid / fatty acid ester comprises lauric acid, or a compound having a lauric acid residue, e.g., coconut oil.The fatty acid and / or fatty acid ester is reacted with a dialkanolamine to provide a dialkanolamide (II). A dialkanolamine contains a hydrogen atom for reaction with the carboxyl or ester group of the fatty acid or fatty acid ester. The dialkanolamine also contains two hydroxy groups for subsequent reaction with propylene oxide and / or butylene oxide. A portion of the dialkanolamine reacts with the fatty acid and / or fatty acid ester to provide ester (Ila) by reaction of a hydroxy group of the dialkanolamine with the fatty acid and / or fatty-acid ester. The amino group is available for a subsequent reaction with propylene oxide and / or butylene oxide to form alkoxylated ester (la).Preferred dialkanolamines contain two or three carbons in each of the two alkanol groups. Therefore, preferred dialkanolamines include diethanolamine, di-isopropylamine, and di-n-propylamine. The most preferred dialkanolamine is diethanolamine.In a preparation of an amide (II) and ester (Ila), the dialkanolamine can be present in an equivalent molar amount to the fatty acid residues in the fatty acid or fatty acid ester. In another embodiment, the dialkanolamine is present in a molar amount different from the moles of fatty acid residues, i.e. a molar excess or deficiency. In a preferred method, the number of moles of dialkanolamine is substantially equivalent to the number of moles of fatty acid residue.As used herein, the term "fatty acid residue" is defined as R7-C(=0). Therefore, a methyl ester of a fatty acid, i.e., R7- C(=O)OCH3, contains one fatty acid residue, and a preferred method utilizes a substantially equivalent number of moles of dialkanolamine to methyl ester. A triglyceride contains three fatty acid residues, and a preferred method utilizes about three moles of dialkanolamine per mole of triglyceride.Typically, the mole ratio of dialkanolamine to fatty acid residue is about 0.3 to about 1 .5. preferably about 0.6 to about 1 .3, and more preferably about 0.8 to about 1 .2 moles of dialkanolamine per mole of fatty acid residue. To achieve the full advantage of the present invention, the mole ratio of dialkanolamine to fatty acid residue is about 0.9 to about 1.1 moles per mole of fatty acid residue.The reaction to prepare an amide (II) and ester (Ila) can be performed in the presence or absence of a catalyst. Typically, a basic catalyst is employed. More particularly, a catalyst can be an alkali metal alcoholate, such as sodium methylate, sodium ethylate, potassium methylate, or potassium ethylate. Alkali metal hydroxides, such as sodium or potassium hydroxide acid, and alkali metal carbonates, such as sodium carbonate or potassium carbonate, also can be used as the catalyst.The amount of catalyst, if present at all, typically is about 0.01 % to about 5% by weight, with respect to the amount of amide (II) and -ester (Ila) to be produced. The reaction temperature to form an amide (II) and ester (Ila) typically is220895W00138 about 50 °C to about 200 °C. The reaction temperature typically is higher than the boiling point of an alcohol, e.g., methanol, and / or water produced during the reaction to eliminate water and / or the alcohol as it is generated in the reaction. Typically, the reaction is performed for about 2 to about 24 hours.The propoxy lation / butoxy lation reaction often is performed under basic conditions, for example by employing a basic catalyst of the type used in the preparation of an amide (II) and ester (Ila). Additional basic catalysts are nitrogencontaining catalysts, for example, an imidazole. N,N-dimethylethanolamine, and N,N-dimethylbenzylamine. It also is possible to perform the alkoxylation reaction in the presence of a Lewis acid, such as titanium trichloride or boron trifluoride.The amount of catalyst utilized is about 0.5% to about 0.7%, by weight, based on the amount of amide (II) and ester (Ila), in total, used in the alkoxylation reaction. In some embodiments, a catalyst is omitted.The temperature of the alkoxylation reaction typically is about 80 °C and about 180 °C. Preferably, the alkoxylation reaction is performed an atmosphere that is inert under the reaction conditions, e.g., nitrogen.The alkoxylation reaction also can be performed in the presence of a solvent. The solvent is inert under the reaction conditions. Suitable solvents are aromatic or aliphatic hydrocarbon solvents, such as hexane, toluene, and xylene. Halogenated solvents, such as chloroform, or ether solvents, such as dibutyl ether and tetrahydrofuran, also can be used.In preferred embodiments, the reaction mixture that yields a dialkanol amide (II) and -ester (Ila) is used without purification in the alkoxylation reaction to provide an alkoxylated amide (I) and alkoxylated ester (la). In another preferred embodiment, the reaction mixture that provides an alkoxylated amide (I) and ester (la) also is used without purification. As a result, a preferred reaction product of the present invention comprises a variety of products including, for example, alkoxylated amide (I), alkoxylated ester (la), dialkanolamide (II), -ester (Ila), unreacted dialkanolamine, by-product hydroxy compounds (e.g. glycerin or other alcohol), mono- and / or di-esters of a starting triglyceride, polyalkylene oxide oligomers, aminoesters, and ester-amides.More details about the process for manufacturing this compound can be found in WO 2010 / 005720.Fatty AcidThe fatty acid as friction modifier is at least one aliphatic monocarboxylic acid having from 12 to 30 carbon atoms, preferably having from 14 to 26 carbon atoms, very preferably having from 16 to 24 carbon atoms, and especially having from 18 to 20 carbon atoms.220895W00139The monocarboxylic acid can be saturated or onefold, twofold or multifold unsaturated, preferably unsaturated, very preferably onefold unsaturated.It is also possible to us a mixture of aliphatic monocarboxylic acids, especially from natural and renewable sources, e.g. animal or preferably vegetable oil. Such mixtures of aliphatic mono-carboxylic acids are usually obtained by saponification of natural oils and yield mixtures of aliphatic monocarboxylic acids with different number of carbon atoms depending on the source and origin of the natural oil. Preferred are linseed oil, coconut fat, palm kernel oil, palm oil, soy bean oil, peanut oil, cocoa butter, shea butter, cotton seed oil, corn oil, sunflower oil, rapeseed oil or castor oil.Examples for aliphatic monocarboxylic acids are dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid, linolaidic acid, erucic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid, preferred are tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid, linolaidic acid, erucic acid, arachidic acid, and behenic acid, very preferred are hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid, and linolaidic acid, and especially oleic acid, linoleic acid, and linolaidic acid. Oleic acid is especially preferred.DehazerSuitable dehazer are, for example, the alkali metal or alkaline earth metal salts of al ky l-substituted phenol- and naphthalenesulfonates and the alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tertpentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example including in the form of EO / PO block copolymers, polyethyleneimines or else polysiloxanes.Further suitable dehazers are EO / PO-based alkoxylates of alkylphenol-formaldehyde condensates (Novolac, resol or calixarene type), EO / PO-based alkoxylates of diols (e.g. propandiol, ethylene glycole), triols (e.g. glycerol or trimethylolpropane), ethylene diamine, or polyethyleneimine. Further suitable dehazers are alkybenzene sulfonic acids, dialkylsulfosuccinates or alkali metal or ammonium salts thereof. Suitable dehazers are described in WO 96 / 22343. Further suitable dehazers based on diglycidyl ethers are described in US 3383326 and US 3511882.Other suitable dehazers are, for example, alkoxy lated phenol-formaldehyde condensates, for example the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).Antioxidants220895W00140Suitable antioxidants are, for example, substituted phenols, such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methyl phenol, 2,4-di-tert-butyl-6-methylphenol, preferably hindered phenols with an ester group bearing radical in paraposition, such as 3-[3,5-bis-(dimethylethyl)-4-hydroxy-phenyl] propanoic acid Ce- to C2o-alkyl esters, e.g. 2- ethylhexyl- or stearylester, and also phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.Metal deactivatorsSuitable metal deactivators are, for example, salicylic acid derivatives such as N, N'-disalicylidene-1 ,2- propanediamine.SolventsSuitable solvents are, for example, nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, white spirit 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, 2- propy I heptanol, decanol, isotridecanol and isoheptadecanol. Such solvents are usually added to the fuel together with the aforementioned additives and coadditives, which they are intended to dissolve or dilute for better handling.Therefore, another object of the present invention is the above-mentioned process for shortening the injection time t of injectors of a direct injection spark ignition engine in which the deposit control additive (DCA) is applied in the form of a fuel additive package for gasoline fuels, comprising- at least one quaternary ammonium salt as deposit control additive,- optionally at least one further deposit control additive selected from the group consisting of- at least one branched primary alkyl amine, the alkyl group having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms and with a branching of at least 1.0, preferably of from 1.0 to 8.0, more preferably from 1.5 to 7.0,- Mannich adducts, and- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, and- optionally at least one further gasoline fuel additive, selected from the group consisting of- friction modifiers- dehazers- antioxidants- metal deactivators- corrosion inhibitors,- carrier oils, and- solvents.220895W00141Preferably the at least one further gasoline fuel additive is selected from the group consisting of corrosion inhbitors, carrier oils, and solvents.FuelsIn the context of the present invention, gasoline fuels mean liquid hydrocarbon distillate fuels boiling in the gasoline range. It is in principle suitable for use in all types of gasoline, including "light" and "heavy" gasoline species. The gasoline fuels may also contain amounts of other fuels such as, for example, ethanol.Typically, gasoline fuels, which may be used according to the present invention exhibit, in addition, one or more of the following features:The aromatics content of the gasoline fuel is preferably not more than 50 volume % and more preferably not more than 35 volume %. Preferred ranges for the aromatics content are from 1 to 45 volume % and particularly from 5 to 35 volume %.The sulfur content of the gasoline fuel is preferably not more than 100 ppm by weight and more preferably not more than 10 ppm by weight. Preferred ranges for the sulfur content are from 0.5 to 150 ppm by weight and particularly from 1 to 10 ppm by weight.The gasoline fuel has an olefin content of not more than 21 volume %, preferably not more than 18 volume %, and more preferably not more than 10 volume %. Preferred ranges for the olefin content are from 0.1 to 21 volume % and particularly from 2 to 18 volume %.The gasoline fuel has a benzene content of not more than 1 .0 volume % and preferably not more than 0.9 volume %. Preferred ranges for the benzene content are from 0 to 1 .0 volume % and preferably from 0.05 to 0.9 volume %.The gasoline fuel has an oxygen content of not more than 45 weight %, preferably from 0 to 45 weight %, and most preferably from 0.1 to 3.7 weight % (first type) or most preferably from 3.7 to 45 weight % (second type). The gasoline fuel of the second type mentioned above is a mixture of lower alcohols such as methanol or especially ethanol, which derive preferably from natural source like plants, with mineral oil based gasoline, i.e. usual gasoline produced from crude oil.Typical ethanol-containing fuel compositions comprise- from 97 to 0 vol% gasoline, preferably 95 to 5, more preferably 92.5 to 10, even more preferably 90 to 15, and especially 85 to 20 %, and- from 3 to 100 vol% ethanol, preferably 5 to 95, more preferably 7.5 to 90, even more preferably 10 to 85, and especially 15 to 80%.220895W00142An example for such gasoline is "E 85", a mixture of 85 volume % of ethanol with 15 volume % of mineral oil based gasoline. Also, a fuel containing 100 % of a lower alcohol, especially methanol or ethanol, is suitable, which is referred to as "E100". Further examples for such gasolines are "E 10", a mixture of 10 volume % of ethanol with 90 volume % of mineral oil based gasoline and "E 20", a mixture of 20 volume % of ethanol with 80 volume % of mineral oil based gasoline.The amount of alcohols and ethers contained in the gasoline may vary over wide ranges. Typical maximum contents are e.g. ethanol 85% by volume, isopropanol 20% by volume, tert-butanol 15% by volume, isobutanol 20% by volume and ethers containing 5 or more carbon atoms in the molecule 30% by volume.Typical methanol-containing fuel compositions comprise- from 97 to 0 vol% gasoline, preferably 95 to 5, more preferably 92.5 to 10, even more preferably 90 to 15, and especially 85 to 20 %, and- from 3 to 100 vol% methanol, preferably 5 to 95, more preferably 7.5 to 90, even more preferably 10 to 85, and especially 15 to 80%.Preferred embodiments of methanol contents of the fuels areM5: 5 vol% methanol and 95 vol% gasoline,M10: 10 vol% methanol and 90 vol% gasoline,M15: 15 vol% methanol and 85 vol% gasoline, M85: 85 vol% methanol and 15 vol% gasoline, M100: 100 vol% methanol.In a preferred embodiment the biobased content of methanol resp. ethanol used in the fuel is greater than 0 (zero), preferably at least 10%, more preferably at least 20%, even more preferably at least 40%, and especially at least 60%.The summer vapor pressure of the gasoline fuel is usually not more than 70 kPa and preferably not more than 60 kPa (at 37°C).The research octane number ("RON") of the gasoline fuel is usually from 90 to 100. A usual range for the corresponding motor octane number ("MON") is from 80 to 90.The above characteristics are determined by conventional methods (DIN EN 228).Therefore, another object of the present invention is the above-mentioned process for shortening the injection time t of injectors of a direct injection spark ignition engine wherein the engine is operated with a gasoline fuel, comprising - at least one quaternary ammonium salt as deposit control additive,220895W00143- optionally at least one further deposit control additive selected from the group consisting of-- at least one branched primary alkyl amine, the alkyl group having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms and with a branching of at least 1.0, preferably of from 1.0 to 8.0, more preferably from 1.5 to 7.0,-- Mannich adducts, and- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, and- optionally at least one further gasoline fuel additive, selected from the group consisting of-- friction modifiers-- dehazers- antioxidants- metal deactivators- corrosion inhibitors,- carrier oils, and- solvents.Preferably the at least one further gasoline fuel additive is selected from the group consisting of corrosion inhibitors, carrier oils, and solvents.Typical concentrations of deposit control additives in the fuel to achieve a shortening of the injection time t depend on the type of deposit control additives and are as follows:In the case of polyalkenemono- or polyalkenepolyamines or Mannich adducts the concentration of the at least one deposit control additive in the fuel is from 10 to 2500 ppm by weight, preferably from 25 to 1000 ppm by weight, more preferably from 50 to 500 ppm by weight (based on the gasoline composition).In the case of branched alkyl amines as deposit control additives the concentration in the fuel is from 10 to 500 ppm, preferably from 15 to 250 ppm, more preferably from 20 to 100 ppm, most preferably from 25 to 50 ppm.In the case of quaternary ammonium compounds the concentration of the at least one deposit control additive in the fuel is from 10 to 100 ppm by weight, preferably of from 20 to 50 ppm by weight (based on the gasoline composition).The one or more corrosion inhibitors, if any, are present in the gasoline fuels normally in an amount of from 0.1 to 10 ppm by weight, preferably of from 0.2 to 8 ppm by weight, more preferably of from 0.3 to 7 ppm by weight, most preferably of from 0.5 to 5 ppm by weight, for example of from 1 to 3 ppm by weight.220895W00144The one or more carrier oils, if any, are present in the gasoline fuels normally in an amount of from 10 to 3.000 ppm by weight, preferably of from 20 to 1000 ppm by weight, more preferably of from 50 to 700 ppm by weight, most preferably of from 70 to 500 ppm by weight.One or more dehazers as additive component, if any, are present in the gasoline fuels generally in an amount of from 0.5 to 100 ppm by weight, preferably of from 1 to 50 ppm by weight, more preferably of from 1 .5 to 40 ppm by weight, most preferably of from 2 to 30 ppm by weight, for example of from 3 to 20 ppm by weight.The other additive components described above each, if any, are present in the gasoline fuels generally in an amount of from 0.5 to 200 ppm by weight, preferably of from 1 to 100 ppm by weight, more preferably of from 1 .5 to 40 ppm by weight, most preferably of from 2 to 30 ppm by weight.The amounts given throughout the text refer to the pure components excluding e.g. solvent, unless stated otherwise.ExamplesQuat 1 : Quaternised dimethyl n-hexadecylamine with propylene oxide with polyisobutylene succinic acid (Mn approx. 1000) as counterion, prepared according to Preparation Example 6 of WO 2014 / 195464 A1, 50% in 2-ethy I hexanol.Example 1 : Determination of injection time with a direct injection spark ignition engine.1. injection time in direct injecting gasoline engines (Direct Injection Spark Ignition (DISI) or Gasoline Direct Injection (GDI))The test method is a preliminary version of the upcoming CEO test for injector fouling in DISI engines (TDG-F-113) and was published by D. Weissenberger, J. Pilbeam, "Characterisation of Gasoline Fuels in a DISI Engine", lecture held at Technische Akademie Esslingen, June 27, 2017. The test engine is a VW EA111 1.4L TSI engine with 125 kW. The test procedure is a steady state test at an engine speed of 2000 rpm and a constant torque of 56 Nm.The test procedure is performed with the following injectors: Magnet! Marell! 03C 906 036 E. Reference oil RL-271 from Haltermann Carless was used as engine oil. The test was run with an EN 228 compliant low sulfur E0 Haltermann DISI TSI fuel according to CEC RF-83 mod complying with EN 228.The keep-clean phase (KC) was run during 48 hours. The additive was a multifunctional package delivering 20 ppm of Quat 1 and 132 mg / kg (65 wt.-% active) of a polyisobutene amine available under the tradename KEROCOM(R) PI BA from BASF SE, Ludwigshafen, to the fuel. The further ingredients of the additive package were carrier oil, corrosion inhibitor, dehazer, and solvent.220895W00145The injection time significantly decreased during the course of the test compared to the initial value. This reduction developed over the first approximately 18 hours and reached its lowest value after this time, which was maintained throughout the remaining period of the test procedure.2. Injection time in direct injecting gasoline engines (Direct Injection Spark Ignition (DISI) or Gasoline Direct Injection (GDI)In the dirty-up-clean-up sequence dirty-up is achieved by running the engine over 48 hours as described for the keep-clean procedure (see above) with base fuel. The relative change of injection time is determined as described above for the keep-clean test. The subsequent clean-up run is done with additized base fuel over 24 h. At the end of the test 3 data points are determined within 15 minutes, which mean value gives the injection time at end of clean-up test. The test result for the clean-up is the relative change of activation time of the injectors relative to the aver-age injection time determined at the end of the dirty-up phaseThe test was run with an EN 228 compliant low sulfur Haltermann DISI TSI fuel according to CEC RF-83 mod complying with EN 228.The dirty-up phase used fuel without additive and was run for 48 hours, the clean-up phase using additized fuel for 24 hours. The additive was a quaternised amine (50 wt.-% active) according to WO 14 / 195464 A1, Example 6 (Quat 1) used at a dosage of 50 mg / kg.At the end of the clean-up phase the injection time was significantly lower than initial value at the beginning of the start-up phase. This reduction developed over the first approximately 17 hours of the clean-up phase and reached its lowest value after this time, which was maintained throughout the remaining period of the test procedure.

Claims

220895W00146Claims1. Process for shortening the injection time t of injectors of a direct injection spark ignition engine below the starting ignition time to, wherein the engine is operated with a gasoline fuel comprising at least one quaternary ammonium salt as deposit control additive (DCA), wherein the starting ignition time to is the injection time determined by the engine control unit (ECU) of the direct injection spark ignition engine in order to achieve the steady state operation conditions with a constant engine speed of 2000 rpm and a constant torque of 56 Nm according to TDG F-113 for the specific gasoline fuel without any additive.

2. Process according to Claim 1 , wherein the quaternary ammonium salt is of the formula+NR1R2R3R4A- in whichA- stands for an anion, preferably a carboxylate R5COO’ or a carbonate R5O-COO’,R1, R2, R3, R4, and R5independently of another are an organic residue with from 1 to 100 carbon atoms, substituted or unsubstituted, preferably unsubstituted, linear or branched alkyl, alkenyl or hydroxyalkyl residue with 1 to 100, more preferably 1 to 75, even more preferably 1 to 30, most preferably 1 to 25 and especially 1 to 20 carbon atoms,R5additionally may be substituted or unsubstituted cycloalkyl or aryl residues bearing 5 to 20, preferably 5 to 12 carbon atoms.

3. Process according to Claim 1 , wherein the quaternary ammonium salt is of the formulawherein in this formula220895W00147RIB stands for a polyisobutenyl residue having a number average molecular weight Mnof from 200 to 2300, preferably from 550 to 1500 and more preferably from 750 to 1300 g / mol,R stands for a hydroxy-Ci- to C4-alkyl, preferably 2-hydroxypropyl.

4. Process according to Claim 1 , wherein the quaternary ammonium salt is of the formulawherein in this formulaRastands for Ci- C2o-alky I , preferably C9- to C -alkyl, more preferably for undecyl, tridecyl, pentadecyl or heptadecyl,Rbstands for a hydroxy-Ci- to C4-alkyl, preferably 2-hydroxy propyl or 2-hydroxybutyl, andA- stands for an anion, preferably carboxylate R5C00-, as defined above, more preferably R5C00- being a carboxylate of a fatty acid, especially A- being acetate, 2-ethyl hexanoate, oleate, polyisobutenyl succinate or monoesters of polyisobutenyl succinate.

5. Process according to Claim 1 , wherein the quaternary ammonium salt is of the formulawherein in this formulaPI B stands for a polyisobutenyl residue having a number average molecular weight Mnof from 200 to 2300, preferably from 550 to 1500 and more preferably from 750 to 1300 g / mol,R stands for an Ci- to C4-alky I or hydroxy-Ci- to C4-alkyl, preferably methyl or 2-hydroxypropyl,Z stands for a hydrocarbyl linker with 2 to 10 carbon units and including one or more carbon units thereof independently replaced with a bivalent moiety selected from the group consisting of -O-, -N(R')-, -C(=O)-, -C(=O)O-, or -C(=O)NR’-;220895W00148R' is independently a hydrogen or a group selected from C1 -6 aliphatic, phenyl, or alkylphenyl, andA- stands for an anion, preferably carboxylate R5COO’ or a carbonate R5O-COO’ as defined above, more preferably acetate, salicylate or methyloxalate, especially salicylate.

6. Process according to Claim 1 , wherein the quaternary ammonium salt is of the formulawherein in this formulaRIB stands for a polyisobutenyl residue having a number average molecular weight Mnof from 200 to 2300, preferably from 550 to 1500 and more preferably from 750 to 1300 g / mol,R stands for an Ci- to Chalky I or hydroxy-Ci- to C^alkyl, preferably methyl or 2-hydroxypropyl, andA- stands for an anion, preferably carboxylate R5COO- or a carbonate R5O-COO- as defined above, more preferably acetate, salicylate or methyl oxalate.

7. Process according to Claim 1 , wherein the quaternary ammonium salt is of the formulawherein in this formulaRaand Rbindependently of another stand for C 1— C2o-al ky I or hydroxy-Ci- to C4-alkyl, preferably Rastands for Ci— C2o-alkyl, preferably ethyl, n-butyl, n-octyl, n-dodecyl, tetradecyl or hexadecyl, and Rbstands for hydroxy-Ci- to C4-alkyl, preferably 2-hydroxypropyl,A- stands for an anion, preferably carboxylate R5COO- or a carbonate R5O-COO- as defined above, more preferably Ci2-Cioo-alkyl- and -alkenyl succinic acid, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid, and polyisobutenyl succinic acid.220895W001498. Process according to any one of Claims 5 to 11 , wherein the quaternary ammonium salts are present in the gasoline fuel in a concentration of from 10 to 100 ppm by weight, preferably of from 20 to 50 ppm by weight.

9. Process according to any one of the preceding claims wherein the gasoline fuel or gasoline fuel additive further to the at least one quaternary ammonium salt as deposit control additive comprises at least one further deposit control additive, selected from the group consisting- branched primary alkyl amines, the alkyl group having from 8 to 22 carbon atoms and a branching of at least1 .0, wherein the degree of branching from is determined from their1H-NMR at 400.33 MHz, wherein the integral from 5 = 2.3 - 2.95 ppm is set to a value of 2 and the signals of the aliphatic methyl groups are integrated from 5 = 0.6 - 0.95 ppm giving the value I (Me), and wherein the degree of branching (ISO index) is calculated according to ISO index = I (Me) / 3 -1,- Mannich adducts, and- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, preferably- Mannich adducts, and- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, and especially- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000.

10. Process according to any one of the preceding claims wherein the gasoline fuel or gasoline fuel additive further to the at least one quaternary ammonium salt as deposit control additive comprises at least one further gasoline fuel additive, selected from the group consisting of- friction modifiers- dehazers- antioxidants- metal deactivators- corrosion inhibitors,- carrier oils, and- solvents.11 . Process according to any one of the preceding claims wherein the gasoline fuel comprises methanol or ethanol.

12. Process according to any one of the preceding claims further improving at least one of the following features:220895W00150- efficiency of combustion, and / or- reduction of emissions of combustion.

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