New additives for diesel fuels

Abstract

The present invention relates to new additives for diesel fuels, their use and diesel fuels containing such new additives.

Description

241031W0011New additives for diesel fuelsDescriptionThe present invention relates to new additives for diesel fuels, their use and diesel fuels containing such new additives.In direct injection diesel engines, the fuel is injected and distributed ultrafinely (nebulized) by a multihole injection nozzle which reaches directly into the combustion chamber of the engine, instead of being introduced into a prechamber or swirl chamber as in the case of the conventional (chamber) diesel engine. The advantage of direct injection diesel engines lies in their high performance for diesel engines and nevertheless low fuel consumption. Moreover, these engines achieve a very high torque even at low speeds.At present, essentially three methods are being used for injection of the fuel directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the pump-nozzle system (unit-injector system or unitpump system), and the common rail system.In the common rail system, the diesel fuel is conveyed by a pump with pressures up to and even over 2000 bar into a high-pressure line, the common rail. Proceeding from the common rail, branch lines run to the different injectors which inject the fuel directly into the combustion chamber. The full pressure is always applied to the common rail, which enables multiple injection or a specific injection form. In the other injection systems, in contrast, only a smaller variation in the injection is possible. Injection in the common rail is divided essentially into three groups: (1.) pre- / pilot-injection, by which essentially softer combustion is achieved, such that harsh combustion noises ("nailing") are reduced and the engine seems to run quietly; (2.) main injection, which is responsible especially for a good torque profile; and (3.) post-injection, which especially ensures a low NOXvalue. In this post-injection, the fuel is generally not combusted, but instead vaporized by residual heat in the cylinder. The exhaust gas / fuel mixture formed is transported to the exhaust gas system, where the fuel, in the presence of suitable catalysts, acts as a reducing agent for the nitrogen oxides NOX.In modern types, the common rail system is capable of multiple injections to optimize combustion profile and emissions.The variable, cylinder-individual injection in the common rail injection system can positively influence the pollutant emission of the engine, for example the emission of nitrogen oxides (NOX), carbon monoxide (CO) and especially of particulates (soot). This makes it possible, for example, for engines equipped with common rail injection systems to meet the Euro 4 standard theoretically even without additional particulate filters.In modern common rail diesel engines, under particular conditions, for example when biodiesel-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal241031W0012compounds are used, deposits can form on the injector orifices, which adversely affect the injection performance of the fuel and hence impair the performance of the engine, i.e. especially reduce the power, but in some cases also worsen the combustion. The formation of deposits is enhanced further by further developments in the injector construction, especially by the change in the geometry of the nozzles (narrower, conical orifices with rounded outlet). For lasting optimal functioning of engine and injectors, such deposits in the nozzle orifices must be prevented or reduced by suitable fuel additives.In the injection systems of modern diesel engines, deposits cause significant performance problems. It is common knowledge that such deposits in the spray channels can lead to a decrease in the fuel flow and hence to power loss. Deposits at the injector tip, in contrast, impair the optimal formation of fuel spray mist and, as a result, cause worsened combustion and associated higher emissions and increased fuel consumption. In contrast to these conventional "external" deposition phenomena, "internal" deposits (referred to collectively as internal diesel injector deposits (IDID)) in particular parts of the injectors, such as at the nozzle needle, at the control piston, at the valve piston, at the valve seat, in the control unit and in the guides of these components, also increasingly cause performance problems. Conventional additives exhibit inadequate action against these IDIDs.The "injection system" is understood to mean the part of the fuel system in motor vehicles from the fuel pump up to and including the injector outlet. "Fuel system" is understood to mean the components of motor vehicles that are in contact with the particular fuel, preferably the region from the tank up to and including the injector outlet.Modern diesel engines with direct injection place high demands on the additivation of fuels, particularly with regard to the suppression or prevention of deposits on the injector nozzles. In order to map the effect of Diesel additives on deposits on the injector nozzles, there is a need for tests with which such deposits can be reproducibly formed under standardised conditions. To this end, in order to meet such a need for new tests, the Coordinating European Council (CEC) recently established a new test standard for direct-injection diesel engines, the CEC F-110 (DW 10C Test, see below) standard for Internal Diesel Injector Deposits, which places further and higher demands on the additives in diesel fuels than the previous standard according to CEC F-98-08 (DW 10B Test).In Europe the Coordinating European Council for the development of performance tests for transportation fuels, lubricants and other fluids (the industry body known as CEC), has developed a new test for additives for modern diesel engines such as HSDI engines. The CEC F-110-23 test is used to assess whether a diesel fuel is suitable for use in engines meeting new European Union emissions regulations known as the "Euro 5" regulations. The test is based on a Peugeot DW10 engine using Euro 5 injectors, and is commonly referred to as DW10C test. This test measures the effects of deposits on the injectors specific to IDIDs with respect to injector sticking.There is now a demand for new additives for diesel fuels that suppress or prevent the formation of deposits on the injector nozzles measured according this new standard in the DW 10C test. It was therefore an object of the present invention to provide further fuel additives which suppress or prevent deposits in the injector tip and internal injector241031W0013deposits in the course of operation of common rail diesel engines. It would be advantageous, however, not strictly necessary if such new additives also perform well in the previous DW 10B test as well as for conventional (chamber) diesel engines, which are still on the market to a considerable extent, such as the XUD9-test. Since additives fulfilling the DW 10B and / or XUD9 test are commercially available on the market the requirements of these tests may still be achieved by combining the new additives with existing DW 10B- and / or XUD9-active additives.The present invention now provides such new additives according to Claim 1.Reaction products of polyisobutenyl succinic acids with polyalkylenamines and subsequently further substituted succinic acid derivatives are known from EP 72645 B1.EP 438849 describes reaction products of polyisobutenyl succinic acids with polyalkylenamines and subsequently other dicarboxylic acids.The products described in these documents are used as dispersants for lubricants. An application in fuels is not disclosed.Reaction products of polyalkylenamines with alkenylsuccinic acids are known from US 5062980. The resulting bis alkenyl succinimides are subsequently reacted with dicarboxylic acids, among others, to obtain cross-linked bis alkenyl succinimides. The products described therein are recommended as dispersants for lubricants and as fuel additives, although the latter application is neither specified in more detail nor supported by examples.US 5551957 A discloses succinimide detergents as reaction products of ethylene polyamines with polyisobutenylsuccinic anhydride in fuel additive concentrates for reducing the formation of intake valve deposits. The polyisobutenylsuccinic anhydride is used in more than stoichiometric amounts with regard to the ethylene poly amines.US 2019 / 0177632 A1 discloses the use of succinimide detergents prepared from the ethylene-propylene copolymers, maleic anhydride, and polyalkylene polyamines. Such succinimide detergents are part of fuel additives to reduce injector nozzle fouling in a diesel internal combustion engine, reduce injector valve deposits in a gasoline internal combustion engine, and / or reduce valve sticking in a gasoline internal combustion engine, however, for the for the succinimide detergents no other effect other than preventing fuel degradation is demonstrated.US 2017 / 0158977 A1 discloses the use of hydrocarbyl-substituted succinic acids for improving the injector performance of a fuel injected diesel engine. An effect on removal of injector deposits (IDID) according to the DW10-C test procedure is disclosed. Reaction products of polyisobutenylsuccinic anhydride and ethylene polyamines are used for comparison and are shown to be less effective than hydrocarbyl-substituted succinic acids.241031W0014US 4747850 A discloses the use of succinimide detergents substituted with a hydroxyhydrocarbyl oxycarbonyl group. An effect in fuels is purported but not proven, only a reduced formation of sludge and varnish deposits in oils is demonstrated.Subject matter of the present invention is the use of a reaction product from the reaction of- 1 equivalent of at least one oligoalkyleneamine (B) with- from 1 to 2 equivalents of at least one Cs-Cwo-alkeny l-substituted succinic acid derivative (A)and subsequent reaction with- at least 1 equivalent of at least one dicarboxylic acid derivative (C) which is different from compound (A) as a detergent additive for diesel fuels.Such reaction products are especially suitable as additives for reducing or preventing Internal Diesel Injector Deposits (IDID) according to the DW 10 C-test method. They furthermore may be active in setups according to XUD9- and / or DW 10 B- test method or may optionally be combined with XUD9- and / or DW 10 B-active additives (see below).The reaction products according to the invention are described in more detail:The reaction product according to the invention is obtainable by reaction of- 1 equivalent of at least one oligoalkyleneamine (B) with- from 1 to 2 equivalents of at least one Cs-Cwo-alkeny l-substituted succinic acid derivative (A)and subsequent reaction with- at least 1 equivalent of at least one dicarboxylic acid derivative (C)and optionally with- at least 1 equivalent of (D) at least one derivative of the optionally substituted salicylic acid or the optionally substituted anthranilic acid.Oliqoalkyleneamine (B)Oligoalkyleneamines (B) are amines bearing from 3 to 10, preferably from 3 to 8, and more preferably from 3 to 6 primary, secondary, and / or tertiary amino groups, wherein the amine preferably bears at least one primary amino group -NH2, wherein the amino groups are connected by (n-1) C2- to Ce-, preferably C2-C4- and more preferably C2-or Cs-alkylene groups, wherein n is the number of amino groups (primary, secondary, and tertiary groups in sum).Preferred examples of alkylene groups are 1 ,2-ethylene-, 1 ,2-propylene- and 1 ,3-propylene-groups, more preferably 1 ,2-ethylene- and 1 ,3-propylene-groups, and even more preferably 1,2-ethylene-groups.241031W0015Oligoethyleneamines are preferably of formulain whichx is a positive integer from 1 to 9, preferably from 1 to 7, and more preferably from 1 to 5, andy is zero or a positive integer of from 1 to 3, preferably 1 or 2.The oligoalkyleneamines comprising at least 4 amino groups may be linear or branched, usually such oligoalkyleneamines are mixtures of linear and branched species.Preferably the oligoalkyleneamine (B) is selected from the group consisting of- diethylenetriamine,- triethylenetetraamine,- tetraethylenepentaamine- pentaethylenehexaamine and- tripropylenetetraamine.Among these oligoalkyleneamines the ethyleneamines are preferred over the propyleneamines.The oligoethyleneamines may comprise cyclic products, i.e. piperazine derivatives, and in the case of triethylenetetramine and higher homologues may further comprise acyclic linear or branched isomers.The content of piperazine derivates is preferably not more than 30 wt%, preferably not more than 25, even more preferably not more than 20, especially not more than 15 and even not more than 10 wt%.241031W0016Preferably, the content of higher or lower homologues in the oligoethyleneamines is not more than 5 wt% each, more preferably not more than 4, and even more preferably not more than 3 wt%.In the case of tetraethylenepentaamine (TEPA) this oligoethyleneamine is principally a mixture of four TEPA ethyleneamines with close boiling points including linear, branched, and two cyclic TEPA products, and higher molecular weight products.These compounds are:- linear TEPA (CAS #000112-57-2, N-(2-aminoethyl)-N'-{2-{(2-aminoethyl)amino}ethyl}-1,2-ethanediamine) - branched AETETA (CAS #031295-46-2, 4-(2-aminoethyl)-N-(2-aminoethyl)-N'-{2-{(2-aminoethyl)amino}ethyl}-1 ,2-ethanediamine)- APEEDA (CAS #031295-54-2, 1-(2-aminoethyl)-4-[(2-aminoethyl)amino]ethyl]-piperazine)- PEDETA (CAS #031295-49-5, 1-[2-[[2-[(2-aminoethyl)amino]ethyl]-amino]ethyl]-piperazine).As pointed out above, the content of cyclic piperazine derivatives in the isomer mixture should be kept as low as possible.Suitable oligoalkyleneamines are commercially available from Dow, Huntsman or BASF.Cs-Cioo-alkenyl-substituted succinic acid derivative (A)The above-mentioned oligoalkyleneamines are reacted with from 1 to 2 equivalents, preferably with 1 to 1.5 equivalents, and more preferably with equimolar amounts of at least one Cs-Cwo-, preferably Ci2-Cwo-alkenyl-substituted succinic acid derivative (A).Such derivatives may be- the anhydride,- the di-Ci-C4-alkyl ester, also mixed alkyl esters are conceivable, preferably methyl or ethyl ester, or- the dicarboxylic acid.Preference is given to anhydrides, diethyl esters, and dimethyl esters, especially anhydrides.The Cs-Cwo-, preferably Cw-Cwo-alkenyl substituent to the succinic acid derivative may be linear or branched, preferably branched, with a double bond in the alkenyl group preferably at the second carbon atom of the alkenyl group. Such alkenyl succinic acid derivatives are e.g. obtainable by ene reaction of a Cs-Cwo-alkene, preferably C12-Cwo-alkene, more preferably of such alkenes with the double bond at the terminal (alpha-) bond or at the beta-bond, with a maleic acid derivate, preferably maleic acid anhydride.241031W0017In a preferred embodiment the Cs-Cwo-alkene preferably Ci2-Cioo-alkene underlying the alkenyl succinic acid derivative is a polymer of ethene, propene, 1 -butene and / or isobutene, preferably of propene or isobutene, and very preferably of isobutene.Preferred alkenes according to this embodiment are dodecene, pentadecene, hexadecene, octadecene, eicosene, heneicosene, tetracosene, and polyisobutenes with a number average molecular weight of from 500 to 1400, preferably from 550 to 1300, more preferably from 600 to 1200, even more preferably from 650 to 1100, and especially from 900 to 1100.Further preferred alkenes are branched dodecenes from propene oligomerisation (tetramer propene) and linear Cs-C30 alkenes derived from ethylene oligomerization, either as o-olefines or isomerized with respect to the double bond to internal olefines, preferably as o-olefines.The preparation of Cs-Cwo-alkeny l-substituted succinic acid derivatives is well known in the prior art and usually occurs via thermal Ene-reaction of the underlying Cs-Cwo-alkene with an appropriate maleic acid derivative, preferably maleic acid anhydride. The corresponding free acid or the esters are usually obtained by hydrolysis of the Cs-Cwo-alkeny l-substituted succinic acid anhydride, the esters by reaction of the anhydride with the corresponding alcohols or - less preferably - by esterification of the acid with such alcohols.Many Cs-Cwo-alkenyl-substituted succinic acid derivatives, especially the anhydrides are commercially available. Especially preferred is Glissopal(R) SA from BASF SE derived from polyisobutene with Mn1000 g / mol and maleic anhydride.Some reaction products of oligoalkyleneamines (B) with 1 equivalent Cs-Cwo-alkeny l-substituted succinic acid derivatives (A) are commercially available and are referred to as polyisobutenylsuccinimides (PIBSI), see below. Such polyisobutenylsuccinimides are preferred starting materials for the subsequent reaction with the dicarboxylic acid (C).It is also possible, albeit less preferable, to use up to 2 equivalents of Cs-Cwo-alkeny l-substituted succinic acid derivative (A) per oligoalkyleneamine so that the product comprises a mixture of alkenylsuccinimides bearing 1 and 2 alkenyl groups per oligoalkyleneamine.Dicarboxylic acid derivative (C)The reaction product of components (A) and (B) is subsequently further reacted with at least 1 equivalent of at least one dicarboxylic acid derivative (C) which is different from compound (A).241031W0018Such derivatives may be- the anhydride,- the di-Ci-C4-alkyl ester, also mixed alkyl esters are conceivable, preferably methyl or ethyl ester, or- the dicarboxylic acid.Preferred are the free dicarboxylic acid and the anhydride, especially the anhydride.The underlying dicarboxylic acid (C) is preferably of the formulaHOOC-R2-COOH,wherein R2may be a single bond, a bivalent Ci- to Cw-alkylene, a bivalent C2- to Cw-alkenylene or Ce- to C -arylene group, each of which may optionally be substituted with Ci- to C2o-alky I- or C2- to C2o-alkenyl-groups. Among the substituents Cs- to C2o-alkenyl-groups are preferred, more preferably Cs-, C12-, C16- and C2o-alkeny l-groups, preferably trimers, tetramers and pentamers of isobutene.Examples for R2are a single bond, 1,1 -methylene, 1 ,2-ethylene, 1 ,3-propylene, 1,4-butylene, 1 ,6-hexylene, 1,8-octylene, 1,10-decylene, 1 ,2-vinylidene, 1,2-phenylene, 1 ,3-phenylene, 1 ,4-phenylene, Ci- to C2o-alkyl-substituted 1 ,2-ethylene and C2- to C2o-alkenyl-substituted 1 ,2-ethylene.Examples for dicarboxylic acids (C) are oxalic acid, malonic acid, succinic acid, dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid.Among these dicarboxylic acid derivatives (C) the 1 ,4-dicarboxylic acids are preferred.More preferably the dicarboxylic acids (C) are selected from the group consisting of succinic acid, Cs-Cwo-, preferably Ci2-Cioo-alkenyl-substituted succinic acid, maleic acid, itaconic acid, and phthalic acid. Even more preferably the dicarboxylic acids (C) are selected from the group consisting of succinic acid, maleic acid and phthalic acid, especially selected from the group consisting of succinic acid and maleic acid.As pointed out above, the dicarboxylic acids preferably are in the form of their anhydrides, if possible.Preferred compounds (C) are succinic acid anhydride, dodecenyl succinic acid anhydride, hexadecenyl succinic acid anhydride, eicosenyl succinic acid anhydride, maleic acid anhydride, itaconic acid anhydride, and phthalic acid anhydride.Compound (C) is different from compound (A), preferably compound (A) is succinic acid anhydride or maleic acid anhydride not bearing further substituents.241031W0019(D) Derivative of optionally substituted salicylic acid or optionally substituted anthranilic acidFurther to compound (C) the reaction product of (A) and (B) may optionally be reacted with at least 1 equivalent of at least one derivative of optionally substituted salicylic acid or optionally substituted anthranilic acid (D).In this case derivative means the free carboxylic acid or a Ci-C4-alkyl ester, preferably methyl or ethyl ester thereof.In case the salicylic acid or anthranilic acid bears a substituent, this may be with Ci- to C2o-alkyl group, e.g. methyl, ethyl, / so-propyl, n-propyl, n-butyl, / so-butyl, sek-butyl, ferf-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.The unsubstituted acids are preferred over the substituted acids and salicylic acid is preferred over anthranilic acid.ReactionThe reaction product of (A) and (B) is reacted with at least 1 equivalent of dicarboxylic acid (C) and optionally with compound (D).For the sake of clarity, the phrase "equivalent" in the context of the present document means "molar equivalents" of one compound with regard to another compound.If p is the number of reactive amino groups in the reaction product of (A) and (B), i.e. primary and secondary amino groups (in sum), and the reaction product of (A) and (B) is reacted with c equivalents of compound (C) and d equivalents of compound (D), it isc + d < p,whereinc is from 1 to p andd is from 0 (zero) to (p - c), preferably d is at least 1.In a preferred embodiment reaction product of (A) and (B) is reacted with compound (C) and optionally compound (D) in a manner that essentially all reactive amino groups are reacted with (C) and optionally (D), preferably at least 90%, more preferably at least 75%, and even more preferably at least 66%.In a preferred embodiment no compound (D) is reacted at all, i.e. d is 0 (zero).241031W00110In case both compounds (C) and (D) are reacted, the molar ratio of compounds (C) and (D) incorporated into the product is from 10 : 1 to 1 : 5, preferably from 5 : 1 to 1 : 2, more preferably from 5 : 1 to 1 : 1, even more preferably from 4 : 1 to 1 : 1 and especially from 4 : 1 to 2 : 1.The reaction of the reaction product of (A) and (B) with compound (C) and optionally (D) usually takes place at a temperature of from 50 °C to 200 °C, preferably from 60 to 180 °C, and more preferably from 70 to 150 °C for a period of from 5 min to 36 hours, preferably from 10 min to 30 hours and more preferably from 15 min to 24 hours, depending on the reaction temperature.The reaction may be conducted neat or preferably in an inert solvent, preferably a solvent which may later be used in the formulation (see below). Preferred solvents are 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). Polar organic solvents are less preferred since they may react with compounds (C) or (D).If required, the reaction can be conducted under pressure.Unreacted compounds, especially (C) or (D) may be distilled off the reaction mixture at reduced pressure or - less preferred - may remain in the reaction mixture. Usually it is aimed for, to completely react the reaction compounds and to achieve essentially complete conversion.The exact product composition of the reaction of compounds (A), (B), and (C) may vary depending on the reaction conditions and especially the stoichiometry of the compounds actually employed during the reaction.In a preferred embodiment the reaction composition comprises a compound according to the general formula (I)and / or241031W001whereinR1is a Cs-Gwo-alkeny I radical,R2is 1 ,2-ethylene, 1- or 2-C8-Cioo-alkenyl-substituted 1 ,2-ethylene or 1 ,2-vinylidene andx is a positive integer 1, 2, 3 or 4.Such compound is especially obtained when compounds (A) and (B) are reacted in approx, equimolar amounts and are subsequently reacted with at least (x + 1) equivalents of dicarboxylic acid derivative (C).In case that at least one compound (D) is included it is a preferred embodiment that the reaction composition comprises a compound according to the general formula (II)R1is a Cs-Cioo-alkeny I radical,241031W00112R2is 1 ,2-ethylene, 1- or 2-Cs-Cioo-alkenyl-substituted 1 ,2-ethylene or 1 ,2-vinylidene,x is a positive integer 1, 2, 3 or 4,R3is hydrogen, Ci- to C2o-alky I or Ci- to C2o-alky loxy , andX is -OH or -NH2.The distribution of the residues within the reaction mixture depends on the stoichiometry of compounds (C) and (D) during the reaction. Further to the compounds represented by the formulae above, the reaction mixture usually comprises analogous compounds in which not all amino groups are reacted with compounds (C) and / or (D).It has been found that reaction products with a certain content of carboxylic acid groups have proven particularly useful for the propose of the invention. Therefore, another subject matter of the present invention is the use of a reaction product from the reaction of- 1 equivalent of at least one oligoalkyleneamine (B) with- from 1 to 2 equivalents of at least one Cs-Gwo-alkenyl-substituted succinic acid derivative (A)and subsequent reaction with- at least 1 equivalent of at least one dicarboxylic acid derivative (C)as a detergent additive for diesel fuels, wherein the reaction product has an acid number of from 50 to 150 mg KOH / g, preferably from 60 to 140, more preferably from 70 to 130, even more preferably from 80 to 130, and especially from 90 to 120 mg KOH / g.The acid number is determined via potentiometric titration at 20 °C in toluene / ethanol 2:1 (v / v) using 0,1 N (0,1 mol / l) KOH in ethanol.Another object of the present invention is the use of the reaction products described above, especially those of formula (I) or (II) in additive packages for fuels.In one embodiment such reaction products, especially those of formula (I) or (II) can be used as constituents in additive packages for Diesel fuels.Accordingly, subject matter of the present invention are additive packages for Diesel fuels, comprising at least one reaction product, especially those of formula (I) or (II) and further comprising at least one further Diesel additive.In another embodiment the at the least one reaction product, especially those of formula (I) or (II) can be used as constituents in additive packages for gasoline fuels.Accordingly, subject matter of the present invention are additive packages for gasoline fuels comprising at least one reaction product, especially those of formula (I) or (II) and further comprising at least further one gasoline additive.241031W00113Typical further additives are described in the following:Diesel additivesAnother aspect of the present invention are additive packages for Diesel fuels, comprising at least one reaction product, especially those of formula (I) or (II) and further comprising at least one Diesel additive, selected from the group consisting of- deposit control additives, selected from the group consisting of- quaternary nitrogen compounds and- polyisobutenylsuccinimides,- dehazers, and- cetane number improvers.Some of these deposit control additives, especially the quaternary nitrogen compounds are known be active in XUD9- and / or DW 10 B-tests. Therefore, it is a preferred embodiment of the present invention to combine the new additives according to the present invention with at least one further deposit control additive, preferably at least one quaternary nitrogen compound, if the activity of the new additives alone in the XUD9- or DW 10 B-test is not sufficient.Other additives, such as solvents, defoamers, colorants, lubricity improvers, cold flow improvers, antioxidants, and fuel markers, may be present.The above-mentioned additives are described in more detail as follows:Quaternary nitrogen compoundsThe at least one quaternary nitrogen component refer, 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".The quaternary ammonium compounds are preferably of the formula241031W00114NR14R15R16R17A-in whichA’ stands for an anion, preferably a carboxylate R18C00’ or a carbonate R180-C00’,andR14, R15, R16, R17, and R18independently 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,R18additionally 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 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- Ci2-cycloalkyl 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 R14to R17may 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 definitions241031W00115Ci-C2o-alkyl 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-cyanopropyl, 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-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxy butyl or 6-ethoxyhexyl, andC2— C2o-alky I 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.241031W00116Furthermore,functional groups can be carboxy, carboxamide, hydroxy, di (Ci-C4-alkyl)amino, Ci-C4-alkyloxycarbonyl, cyano or Ci-C4-alkyloxy,Ce— Ci2-ary I 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, hexyloxyphenyl, 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 R14to R18are preferably C2-Ci8-alkyl or C6-Ci2-aryl, more preferably C4-Ci6-alkyl or C6-Ci2-aryl, and even more preferably C4-Ci6-alkyl or Ce-aryl.The residues R14to R18may be saturated or unsaturated, preferably saturated.Preferred residues R14to R18do not bear any heteroatoms other than carbon of hydrogen.Preferred examples of R14to R17are 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.241031W00117In a preferred embodiment at least one of the residues R14to R17is selected from the group consisting of 2-hydroxyethyl, hydroxyprop-1 -yl, hydroxyprop-2-yl, 2-hydroxybutyl or 2-hydroxy-2-phenylethyl.In one embodiment R18is 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 10000, 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-propy lheptanoic 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 inWO 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;241031W00118WO 2011 / 095819 A1, page 4, line 5 to page 9, line 29;GB 2496514 A, paragraph

[0012] 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; andWO 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, EP 2674471 B1, paragraphs

[0018] to

[0024] and

[0045] to

[0048] ,EP 4141091 B1, paragraphs

[0012] to

[0042] and

[0053] to

[0068] ,WO 2008 / 27881, page 6, line 13 to page 10, line 3, and page 20, line 1 to line 18,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 550 to 2300, preferably from 650 to 1500 and more preferably from 750 to 1300 g / mol,R stands for an Ci- to Chalky I or hydroxy-Ci- to C4-alkyl, preferably methyl or 2-hydroxypropyl, andA’ stands for an anion, preferably carboxylate R18COO’ or a carbonate R18O-COO’ as defined above, more preferably acetate, salicylate or methyl oxalate.In one embodiment the quaternized ammonium compound is a betaine of formula241031W00119wherein in this formulaRIB stands for a polyisobutenyl residue having a number average molecular weight Mnof from 550 to 2300, preferably from 650 to 1500 and more preferably from 750 to 1300 g / mol.In another preferred embodiment the quaternized ammonium compound is of formulawherein in this formulaRIB stands for a polyisobutenyl residue having a number average molecular weight Mnof from 550 to 2300, preferably from 650 to 1500 and more preferably from 750 to 1300 g / mol,R stands for a hydroxy-Ci- to C4-alkyl, preferably 2-hydroxy propyl.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 550 to 2300,241031W00120preferably from 650 to 1500 and more preferably from 750 to 1300 g / mol,R stands for an Ci- to Chalky I or hydroxy-Ci- to C4-alkyl, preferably methyl, andA’ stands for an anion, preferably carboxylate R18COO’ or a carbonate R18O-COO’ as defined above, more preferably salicylate or methyl oxalate.In another embodiment the quaternized ammonium compound is of formulawherein in this formulaRastands for Ci— C2o-alkyl, 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 R18C00’, as defined above, more preferably R18C00’ being a carboxylate of a fatty acid, especially A’ being acetate, 2-ethylhexanoate, oleate or polyisobutenyl succinate.In another embodiment the quaternized ammonium compound is a betaine of formulawherein in this formulaRastands for Ci- C2o-alkyl , preferably C9- to C -alkyl, more preferably for undecyl, tridecyl, pentadecyl or heptadecyl.In one embodiment the quaternized ammonium compound is of formulawherein in this formula241031W00121Xj for i = 1 to n and 1 to m 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-,m and n independently of another are positive integers, with the proviso that the sum (m + n) 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 R18COO’ or a carbonate R18O-COO’ as defined above, more preferably salicylate or methyl oxalate.In another preferred embodiment the quaternized ammonium compound is of formulawherein in this formulaRaand Rbindependently of another stand for Ci— C2o-alky I 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 R18COO’ or a carbonate R18O-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.In another preferred embodiment the quaternized ammonium compound is of formula241031W00122or of formulawhereinR30is 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" polyisobutene radical,R31is hydrogen, methyl, ethyl, iso-propyl, n-butyl, tert-butyl, but-2-yl, or amyl, preferably hydrogen or methyl, and more preferably methyl,R32and R33independently 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 R32and R33together the nitrogen atom form a five- or six-membered ring, preferably a pyrrolidine, piperidine or morpholine ring,R34is bivalent organic, preferably 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, 3-oxa-1,5-pentylene, and 1 ,6-hexylene, and especially being 1,2-ethylene or 1 ,3-propylene,R35is Ci-C6alkyl, preferably methyl, 2-hydroxy-C8-Ci2-aralkyl or 2-hydroxy-C2-Ci2-alkyl, preferably 2-hydroxy-propyl, R36is hydrogen or Ci-Ce-alkyl, -(CH2)3-NR32R33, -(CH2)3-phenyl(R30)(R31)(OH), or together with the phenolic oxygen a -C(=O)- group or a -CH2- group forming a ring structure with the oxygen atom attached to the aromatic ring, and A’ stands for an anion, preferably carboxylate R18COO’ or a carbonate R18O-COO’ as defined above, more preferably salicylate or methyloxalate.241031W00123PolyisobutenylsuccinimidesPolyisobutenylsuccinimides are of formulawherein in this formulaRIB stands for a polyisobutenyl residue having a number average molecular weight Mnof from 550 to 2300, preferably from 650 to 1500 and more preferably from 750 to 1300 g / mol, andn stands for a positive integer of from 2 to 6, preferably 2 to 5, and more preferably 3 or 4.Among the deposit control agents quaternary nitrogen compounds are preferred over the polyisobutenylsuccinimides.DehazersDehazers as additive components are preferably selected from- alkoxy lation copolymers of ethylene oxide, propylene oxide, butylene oxide, styrene oxide and / or other oxides, e.g. epoxy based resins; and- alkoxylated phenol formaldehyde resins- cross-linked polyol demulsifiers obtained from reacting an ethylene oxide - propylene oxide - containing polymer with a diepoxide, such as bisphenol A diglycidyl ether, optionally followed by further alkoxlation with ethylene oxide and / or propylene oxide.Such dehazer components are normally commercially available products, e.g. the dehazer products available from Baker Petrolite under the brand name of Tolad® such as Tolad® 2898, 9360K, 9348, 9352K, 9327 or 286K.Cetane number improvers241031W00124Cetane number improvers used are typically organic nitrates. Such organic nitrates are especially nitrate esters of unsubstituted or substituted aliphatic or cycloaliphatic alcohols, usually having up to about 10, in particular having 2 to 10 carbon atoms. The alkyl group in these nitrate esters may be linear or branched, and saturated or unsaturated. Typical examples of such nitrate esters are methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, n-amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, tert-amyl nitrate, n-hexyl nitrate, n-heptyl nitrate, sec-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, sec-octyl nitrate, n-nonyl nitrate, n-decyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate and isopropylcyclohexyl nitrate and also branched decyl nitrates of the formula RaRbCH-CH2-O-NO2 in which Rais an n-propyl or isopropyl radical and Rbis a linear or branched alkyl radical having 5 carbon atoms, as described in WO 2008 / 092809. Additionally suitable are, for example, nitrate esters of alkoxy-substituted aliphatic alcohols such as 2-ethoxyethyl nitrate, 2-(2-ethoxy-ethoxy)ethyl nitrate, 1 -methoxy propyl nitrate or 4-ethoxybutyl nitrate. Additionally, suitable are also diol nitrates such as 1,6-hexamethylene dinitrate. Among the cetane number improver classes mentioned, preference is given to primary amyl nitrates, primary hexyl nitrates, octyl nitrates and mixtures thereof.Most preferably, 2-ethylhexyl nitrate is present in the fuel oils as the sole cetane number improver or in a mixture with other cetane number improvers.Such fuel additive concentrates suitable for use in Diesel fuel, usually comprise0.01 to 40% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight, of at least one reaction product, especially those of formula (I) or (II);0 to 40% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, of at least one compound selected from the group consisting of- quaternary nitrogen compounds and- polyisobutenylsuccinimides;0 to 5% by weight, preferably 0.01 to 5 by weight, more preferably 0.02 to 3.5% by weight, most preferably 0.05 to 2% by weight, of at least one dehazer selected from- alkoxy lation copolymers of ethylene oxide, propylene oxide, butylene oxide, styrene oxide and / or other oxides, e.g. epoxy based resins, and- alkoxylated phenol formaldehyde resins;0 to 75% by weight, preferably 5 to 75% by weight, more preferably 10 to 70% by weight, of at least one cetane number improver;241031W001250 to 50% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight, of at least one solvent or diluent.In each case, the sum of all components results in 100%.Gasoline additivesAnother aspect of the present invention are additive packages for gasoline fuels, comprising at least one reaction product, especially those of formula (I) or (II) and further comprising at least one gasoline additive, selected from the group consisting of- deposit control additives, selected from the group consisting of- quaternary nitrogen compounds,- Mannich adducts, and- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, - corrosion inhibitors, and- carrier oils.The deposit control additives are preferably selected from the group consisting of- quaternary nitrogen compounds, and- polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000Other additives, such as friction modifier, dehazers, antioxidants, metal deactivators, and solvents may be present.The above-mentioned additives are described in more detail as follows:Quaternary nitrogen compoundsAs quaternary nitrogen compounds the same compounds as described for the Diesel additive packages may be used also in gasoline additive packages, the same preferences apply.Mannich adductsTypical Mannich adducts 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.In a preferred embodiment the Mannich adducts are obtainable as described in US 8449630 B2, column 7, line 35 to column 9, line 52.241031W00126Preferably 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, cyclodecylaminedi-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.In 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 B2.241031W00127In a preferred embodiment the Mannich adduct is of formulawhereinR30is 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" polyisobutene radical,R31is hydrogen, methyl, ethyl, iso-propyl, n-butyl, tert-butyl, but-2-yl, or amyl, preferably hydrogen or methyl, and more preferably methyl,R32and R33independently 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 R32and R33together the nitrogen atom form a five- or six-membered ring, preferably a pyrrolidine, piperidine or morpholine ring, and R34is bivalent organic, preferably 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, 3-oxa-1,5-pentylene, and 1 ,6-hexylene, and especially being 1,2-ethylene or 1 ,3-propylene.Polyalkenemono- or polyalkenepolyaminesPolyalkenemono- or polyalkenepolyamines 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. Such241031W00128additives 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 244616. 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 19620262.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 typePolymerwhich 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.241031W00129Particularly 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.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), - alkyl or alkenyl substituted succinic acids, esters or hemiesters, and- olefin-carboxylic acid copolymers (see below).Alkyl or alkenyl substituted succinic acids, esters or hemiestersThe succinic acids, esters or hemiesters are preferably substituted with Cs- to Cwo-alkyl or -alkenyl radicals.241031W00130In a preferred embodiment the succinic acids or hemiesters follow formulawhereinR20is a Cs- to Cwo-alky I or Cs- to Cwo-alkenyl group, preferably Cs- to Cwo-alkenyl, more preferably C12- to Cgo-alkenyl, and even more preferably C16- to Cso-alkeny I group, andR21is hydrogen or Ci- to Cgo-alkyl or C2- to C4-hydroxyalkyl, preferably hydrogen.The underlying succinic acid anhydrides are obtainable by thermal ene reaction of Cs- to Cwo-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) and(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,241031W00131(Ade) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-viny llactams,(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 ferf-butyl, preferably methyl and ethyl, more preferably methyl.Examples of a, p-ethy lenically 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-ethylenically 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-d icarboxy I ic anhydride.241031W00132Examples of a, p-ethy lenically unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, crotonic 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-methyl maleic 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 a-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.Named examples of o-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.241031W00133In 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. The 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.241031W00134In 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.The 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,241031W00135(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-viny llactams,(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-carboxy lie 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-dimethy 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-ethylhexanol.Preferred (meth)acrylic esters (Adc) are (meth)acrylic esters of C5- to Ci2-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, ferf-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.Examples of N-vinylamides or N-vinyllactams (Ade) are N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and N-vinylcaprolactam.Examples of ethy lenical ly unsaturated aromatics (Adf) are styrene and o-methylstyrene.241031W00136Examples of a, p-ethy lenical ly 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.Reaction step (II) is obligatory in case the copolymer obtained from reaction step (I) does not comprise free carboxylic acid groups.Hydrol ization of anhydride groups is preferred over saponification of ester groups.241031W00137Preferably, 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.The 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.241031W00138Should 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 at 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 oils241031W00139Carrier 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 internalolefins), (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 C4-al kylene 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 Cao-alky 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 356725, EP-A 700985 and US-A 4,877,416. For example, the polyetheramines used may be poly-C2- to Ce-alky lene 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 3838918. 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.Further suitable carrier oil systems are described, for example, in DE-A 3826608, DE-A 41 42241, DE-A 4309074, EP-A 452328 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 propylene241031W00140oxide, 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 C -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-G -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 Cato 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 102913.Particular carrier oils are synthetic carrier oils, particular preference being given to the above-described alcohol-started polyethers.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.DehazerSuitable dehazer are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol- and naphthalenesulfonates and the alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds241031W00141such 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 al ky Iphenol-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, alkoxylated phenol-formaldehyde condensates, for example the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).AntioxidantsSuitable 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-propylheptanol, 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.Subject matter of the present invention is also a fuel additive concentrate suitable for use in gasoline fuels comprising0.01 to 40% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight, of the at least one reaction product, especially those of formula (I) or (II);241031W0014210 to 70% by weight, preferably 15 to 60% by weight, more preferably 20 to 50% by weight, of the at least one deposit control agent;0.25 to 5% by weight, preferably 0.5 to 5 by weight, more preferably 0.75 to 3.5% by weight, most preferably 1.0 to 2% by weight, of at least one corrosion inhibitor;0 to 80% by weight, preferably 5 to 60% by weight, more preferably 10 to 40% by weight, of at least one carrier oil;0 to 80% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight, of at least one solvent or diluent; and0 to 15% by weight, preferably 0.5 to 10 by weight, more preferably 1 to 8% by weight, most preferably 3 to 7% by weight, of each of the other additive components described above, if any;with the proviso that the sum of components always results in 100%.Diesel FuelsDiesel fuels or middle distillate fuels are typically mineral oil raffinates which generally have a boiling range from 100 to 400°C. These are usually distillates having a 95% point up to 360°C or even higher. However, these may also be what is called "ultra low sulfur diesel" or "city diesel", characterized by a 95% point of, for example, not more than 345°C and a sulfur content of not more than 0.005% by weight, or by a 95% point of, for example, 285°C and a sulfur content of not more than 0.001% by weight. In addition to the diesel fuels obtainable by refining, the main constituents of which are relatively long-chain paraffins, those obtainable in a synthetic way by coal gasification or gas liquefaction ["gas to liquid" (GTL) fuels] are suitable, too. Also suitable are mixtures of the aforementioned diesel fuels with renewable fuels (biofuel oils) such as biodiesel or bioethanol. Of particular interest at present are diesel fuels with low sulfur content, i.e. with a sulfur content of less than 0.05% by weight, preferably of less than 0.02% by weight, particularly of less than 0.005% by weight and especially of less than 0.001% by weight of sulfur.In a preferred embodiment, the at least one reaction product, especially those of formula (I) or (II) is used together with at least one Diesel additive as described in Diesel fuels which comprise(a) to an extent of 0.1 to 100% by weight, preferably to an extent of 0.1 to less than 100% by weight, especially to an extent of 10 to 95% by weight and in particular to an extent of 30 to 90% by weight at least one biofuel oil based on fatty acid esters, and(b) to an extent of 0 to 99.9% by weight, preferably to an extent of more than 0 to 99.9% by weight, especially to an extent of 5 to 90% by weight, and in particular to an extent of 10 to 70% by weight, of middle distillates of fossil241031W00143origin and / or of synthetic origin and / or of vegetable and / or animal origin, which are essentially hydrocarbon mixtures and are free of fatty acid esters.The at least one reaction product, especially those of formula (I) or (II) may in another preferred embodiment also be used together with at least one Diesel additive as described in Diesel fuels which consist exclusively of middle distillates of fossil origin and / or of synthetic origin and / or of vegetable and / or animal origin, which are essentially hydrocarbon mixtures and are free of fatty acid esters.Diesel fuel component (a) is usually also referred to as "biodiesel". This preferably comprises essentially alkyl esters of fatty acids which derive from vegetable and / or animal oils and / or fats. Alkyl esters typically refer to lower alkyl esters, especially Ci- to Chalky I esters, which are obtainable by transesterifying the glycerides which occur in vegetable and / or animal oils and / or fats, especially triglycerides, by means of lower alcohols, for example, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol or especially methanol ("FAME").Examples of vegetable oils which can be converted to corresponding alkyl esters and can thus serve as the basis of biodiesel 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, to alkyl esters, and thus for them to serve as the basis of biodiesel.Vegetable fats can in principle likewise be used as a source for biodiesel, but play a minor role.Examples of animal oils and fats which can be converted to corresponding alkyl esters and can thus serve as the basis of biodiesel 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, which usually have 12 to 22 carbon atoms and may bear an additional functional group such as hydroxyl groups, and which occur in the alkyl esters, are especially lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, elaidic acid, erucic acid and / or ricinoleic acid.Typical lower alkyl esters based on vegetable and / or animal oils and / or fats, which find use as biodiesel or biodiesel components, are, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME"), tallow methyl ester ("TME"), and especially rapeseed oil methyl ester ("RME").241031W00144However, it is also possible to use the monoglycerides, diglycerides and especially triglycerides themselves, for example castor oil, or mixtures of such glycerides, as biodiesel or components for biodiesel.In the context of the present invention, the Diesel fuel component shall be understood to mean the abovementioned middle distillate fuels, especially diesel fuels, especially those which boil in the range from 120 to 450°C.The Diesel fuels according to the present invention comprise said at least one reaction product, especially those of formula (I) or (II) in an amount of from 5 to 500 ppm, preferably from 10 to 200 ppm, more preferably from 15 to 150 ppm, most preferably from 20 to 100 ppm. Unless explicitly specified otherwise the amounts given in this document refer to the active ingredients excluding e.g. solvent.The deposit control agent or mixture of a plurality of such additives is present in the Diesel fuels in the case of polyisobutenylsuccinimides typically in an amount of from 10 to 1000 ppm by weight, preferably of from 25 to 500 ppm by weight, more preferably of from 50 to 250 ppm by weight.In the case of quaternary ammonium compounds as deposit control agents they are typically present in the Diesel fuels in an amount of from 10 to 100 ppm by weight, preferably of from 20 to 75 ppm by weight,One or more dehazers as additive component, if any, are present in the Diesel 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 Diesel 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.Gasoline 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 "severe" 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 %.241031W00145The 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. An 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 ethanol, is suitable.The amount of alcohols and ethers contained in the gasoline may vary over wide ranges. Typical maximum contents are e.g. methanol 15% by volume, 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.The summer vapor pressure of the gasoline fuel is usually not more than 70 kPa and preferably not more than 60 kPa (at37°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).The gasoline fuels according to the present invention comprise said at least one reaction product, especially those of formula (I) or (II) in an amount of from 5 to 3000 ppm, preferably from 10 to 500 ppm, more preferably from 10 to 250 ppm, most preferably from 15 to 100 ppm.The deposit control agent or mixture of a plurality of such additives is present in the gasoline fuels in the case of polyalkenemono- or polyalkenepolyamines or Mannich adducts typically in an amount of from 10 to 1000 ppm by weight, preferably of from 25 to 500 ppm by weight, more preferably of from 50 to 250 ppm by weight.241031W00146In the case of quaternary ammonium compounds as deposit control agents they are typically present in the gasoline fuels in an amount of from 10 to 100 ppm by weight, preferably of from 20 to 50 ppm by weight,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.The 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.UsesThe additives according to the present invention are surprisingly effective in common rail diesel engines and are notable for their particular suitability as an additive for reducing power loss resulting from external deposits and cold start problems resulting from internal deposits, preferably for reducing or preventing deposits Internal Diesel Injector Deposits (IDID), especially for reducing or preventing deposits as measured according to the DW 10 C-test method and optionally furthermore according to the XUD9- and / or DW 10 B-test method.Subject matter of the present invention is a process for reducing or preventing Internal Diesel Injector Deposits (IDID) according to the CEC F-110-23-test method and optionally according to the CEC F-23-1-01 and / or CEC-F-98-08-test wherein a Diesel engine is operated with a Diesel fuel comprising an effective amount of at least one of the reaction products according to the present invention optionally in combination with further Diesel fuel additives.Furthermore, the reaction products are effective against internal deposits (referred to collectively as internal diesel injector deposits (IDID)) in particular parts inside the injectors, such as at the needle, at the control piston, at the valve piston, at the valve seat, in the control unit and in the guides of these components. Such deposits may be especially wax or soap-like deposits and / or carbon-like polymeric deposits. The IDIDs occur either in the form of wax-or soap-like deposits (fatty acid residues and / or C12- or C -alkyl succinic acid residues detectable analytically) or in241031W00147the form of polymeric carbon deposits. The soap-like deposits inside the fuel injector may often be sodium-, potassium-, and / or calcium-based deposits.These additives furthermore improve the injector cleanliness of gasoline direct injection engines.The reaction products are furthermore effective as an additive for reducing or suppressing the formation of at least one of inlet valve deposits (or intake valve deposits), exhaust valve deposits, combustion chamber deposits, piston top deposits (or piston crown deposits), cylinder head deposits, and injector nozzle fouling. They can also reduce or suppress or influence particulate formation in the exhaust gas, or can reduce or suppress or remove deposit formation within the exhaust gas recirculation system or the exhaust system, especially in exhaust gas aftertreatment devices such as exhaust gas catalysts and diesel particulate filters.Therefore, another subject matter of the present invention is a process for reducing or suppressing or influencing particulate formation in the exhaust gas, or reducing or suppressing or removing deposit formation within the exhaust gas recirculation system or the exhaust system, especially in exhaust gas aftertreatment devices such as exhaust gas catalysts and diesel particulate filters wherein a Diesel engine is operated with a Diesel fuel comprising an effective amount of at least one of the reaction products according to the present invention optionally in combination with further Diesel fuel additives.Furthermore, these reaction products easily form formulations in additive packages or fuels and have a reduced tendency to demix so that the storage stability of the additive packages is improved and / or the amount of solvents for the preparation of formulations may be reduced.Especially in gasoline the reaction products furthermore exhibit an anti-corrosion activity, especially against corrosion of steel, cast iron, and iron-containing alloys.The amounts given throughout the text refer to the pure components excluding e.g. solvent, unless stated otherwise.ExamplesMaterials and methodsPIBSA: Polyisobutylene succinic anhydride, Glissopal® SAF from BASF SE obtained from thermal maleination of HR PIB (Mn1000 g / mol, Glissopal® 1000) with maleic anhydride. Saponification number 91 mg KOH / g, M = 1233 g / mol. TEPA: Tetraethylene pentamine (CAS 112-57-2, M = 189,3 g / mol) from AldrichSuccinic anhydride (M = 100 g / mol) from AldrichMaleic anhydride (M = 98 g / mol) from BASF SESolvent Naphtha ND: Hydrosol A200 ND von DHC Solvent Chemie GmbH241031W00148DDSA: dodecenyl succinic anhydride isomeric mixture (CAS 26544-38-7, from propylene tetramer), saponification value 359 mg KOH / g, M = 312 g / mol, from Aldrich.Tri-1 ,3-propylenetetramine (TPTA, CAS 4605-14-5), M = 188.3 g / mol.Amine numbers were determined according to DIN EN 13716.Acid values were determined via potentiometric titration in toluene / ethanol 2:1 (v / v) using 0,1 N (0,1 mol / l) KOH in ethanol. Titrations were done in triplicates and mean values are reported.DW-10-C Test modified (DW10C inhouse, based on CEC F-110-23)In this test thermocouples are positioned in the engine to enable the exhaust temperature of each cylinder to be measured. This, in conjunction with other measured parameters, allows injector sticking to be tested.The engine of the injector fouling test is the PSA DW10CTED4 / E5. In summary, the engine characteristics are:Design: Four cylinders in line, overhead camshaft, turbocharged with EGRCapacity: 1997 cm3Combustion chamber: Four valves, bowl in piston, wall guided direct injectionPower: 120 kW at 3750 rpmTorque: 340 Nm at 2000 rpmInjection system: Common rail with piezo electronically controlled 6-hole injectors. Max. pressure: 1600 bar (1.6 x 108Pa). Proprietary design by DelphiEmissions control: Conforms with Euro V limit values when combined with exhaust gas post- treatment system (DPF)This engine was chosen as a design representative of the modern European high-speed direct injection diesel engine capable of conforming to present and future European emissions requirements. The common rail injection system uses a highly efficient nozzle design with rounded inlet edges and conical spray holes for optimal hydraulic flow. This type of nozzle, when combined with high fuel pressure has allowed advances to be achieved in combustion efficiency, reduced noise and reduced fuel consumption, but are sensitive to influences that can cause injector sticking.The test is run with current injector design conforming to Euro V injector technology.Full details of the CEC F-110-23 test method can be obtained from the CEC. The test cycle is summarised below: 1. Warm-Up stages:241031W001492. Main RunThe test procedure (CEC F-110-23 issue 2) consists of alternating sequences of soak periods followed by cold starts preceding main run cycles of engine operation. There are 5 main runs and 6 cold starts.If the engine should fail to start or stall during engine operation and cannot be restarted, the test is aborted.During the test ECU parameters are recorded together with exhaust temperatures to evaluate any indication of injector sticking. These parameters contribute to an overall demerit rating at the conclusion of the test.The base fuel for the test was CEC base fuel RF-79-07.For the following results, the CEC F-110-23 method was adjusted, to shorten the test time. Thus, only 3 main runs of 6h each, and 4 cold starts (one before the first main run, and cold start after each main run) were carried out. To still have severe test conditions, despite the shortened test time, the concentrations of the contaminants that are added to the fuel were raised, in respect to the CEC F-110-23 method: instead of 0.5ppm sodium and 10ppm dodecenyl succinic acid (DDSAcid) , in the inhouse method 0.75ppm sodium and 15ppm DDSAcid were used.Results are calculated according to CEC F-110-23 ("new rating”) or CEC F-110-16 ("old rating”), but accounted for the main run numbers that is reduced from 5 in the CEC F-110 method to 3 in the inhouse test variant (i.e. maximum merits of 3 times 5 in cold start exhaust temperatures, maximum merits of 3 times 5 in the main run for pedal position correction and for injector balancing correction, leading to maximum overall merits of 45 in the inhouse test, which translates into a maximum rating of 10 (indicating no IDID effects in the test).Preparative Examples.Example 1A double-walled glass reactor with condenser, dosing unit, overhead stirrer, and nitrogen inlet was charged with PIBSA (512.2 g, 0.4154 mol). After heating to 125 °C TEPA (78.64 g, 0.4154 mol) was added within 50 min. The reaction mixture was heated to 170°C within 1 h and a N2 gas flow (10 L / h) was passed over the reaction mixture to aid water removal. Water was removed for 3 h at 170°C.241031W00150ATR-IR confirmed imide formation. The product had a theoretical molecular weight Mnof 1404 g / mol (amine number determined 133.2 mg KOH / g, theoretically 160 mg KOH / g).Example 2 (inventive):The product from Ex. 1 (230.1 g, 0.1639 mol) was dissolved in 230.1 g Solvent Naphtha ND and succinic anhydride (51.51 g, 0.5151 mol, 3.14 eq.) was added in 4 portions while stirring at 70°C for 30 h. The reaction mixture was heated for further 4h at 90°C and 4 h at 120°C.Consumption of succinic anhydride was followed by ATR-IR.The reaction product had an acid value of 57.5 mg KOH / g (theory 56.5 mg KOH / g), which calculates to 104.5 mg KOH / g with respect to active compound. The active content was adjusted to 50% by addition of 51.51 g Solvent Naphtha ND and the product was filtered using a pressure strainer with filter Seitz® K 900 from Pall.Example 3 (inventive):The product from Ex. 1 (216.8 g, 0.1544 mol) was dissolved in 216.8 g Solvent Naphtha ND and maleic anhydride (50.48 g, 0.5151 mol, 3.34 eq.) was added in 4 portions while stirring at 65-70°C for 24 h. The reaction mixture was heated for further 4h at 90°C and 4 h at 120°C.Consumption of maleic anhydride was followed by ATR-IR.The reaction product had an acid value of 56.2 mg KOH / g (theory 59.7 mg KOH / g), which calculates to 101.8 mg KOH / g with respect to active compound. The active content was adjusted to 50% by addition of 50.48 g Solvent Naphtha ND.Example 4 (inventive):The product from Ex. 1 (137.1 g, 97.65 mmol) was dissolved in 101.0 g Solvent Naphtha ND and DDSA (112.5 g, 0.3606 mol, 3.69 eq.) was added in 4 portions while stirring at 70°C for 13 h. The reaction mixture was heated for further 3 h at 95°C.Consumption of DDSA was followed by ATR-IR.The reaction product had an acid value of 73.7 mg KOH / g (theory 57.7 mg KOH / g), which calculates to 103.5 mg KOH / g with respect to active compound. The active content was adjusted to 50% by addition of 148.6 g Solvent Naphtha ND.Example 5 (comparative):Compound A4 from WO 2018 / 178674: C2o-24-alkenyl succinic acid mono esterified with 2-ethylhexanol.Example 6 (comparative):241031W00151Compound A26 from WO 2020 / 058672, quaternary ammonium compound prepared from reagents C2o-24-alkenyl succinic acid, 1 ,3-butanediol, dimethylethanolamine, 2-ethylhexyl glycidyl ether.Example 7 (comparative):Inventive Ex. 3 from EP 2960319 B1, quaternary ammonium compound prepared from reacting oleylamidopropyl trimethyl ammonium methylcarbonate with 1000 Mw polyisobutenylsuccinic mono 2-ethyhexyl ester mono acid.Example 8:A double-walled glass reactor with condenser, dosing unit, overhead stirrer, and nitrogen inlet was charged with PIBSA (307.6 g, 0.2495 mol). After heating to 125°C TPTA (46.98 g, 0.2495 mol) was added within 50 min. The reaction mixture was heated to 170°C within 1 h and an N2 gas flow (10 L / h) was passed over the reaction mixture to aid water removal. Water was removed for 3 h at 170°C.ATR-IR confirmed imide formation.The product had a theroretical molecular weight Mnof 1403 g / mol (amine number 101.2 mg KOH / g, theoretically 120 mg KOH / g).Example 9 (inventive):The product from Ex. 8 (166.3 g, 0.1185 mol) was dissolved in 166.3 g Solvent Naphtha ND and succinic anhydride (30.0 g, 0.300 mol, 2.53 eq.) was added in 3 portions while stirring at 90°C for 25 min. The reaction mixture was heated for further 5 h at 90°C.Consumption of succinic anhydride was followed by ATR-IR.The reaction product had an acid value of 46.4 mg KOH / g (theory 46.4 mg KOH / g), which calculates to 85.7 mg KOH / g with respect to active compound. The active content was adjusted to 50% by addition of 30.0 g Solvent Naphtha ND.Example 10 (comparative):Polyisobutenyl-substituted succinic acid based on a polyisobutene-derived group with a molecular weight Mw of 1000 g / mol was used according to Inventive Example 12 of US 2017 / 0158977 A1.Application Test Examples.DW10C test results241031W00152US 2017 / 0158977 A1 discloses polyisobutenyl-substituted succinic acid as superior over reaction products of polyisobutenylsuccinic anhydride and ethylene polyamines (cf. US 2017 / 0158977 A1, Table 2, Inventive Example 12 vs. Comparative Examples 7 and 8) in Peugeot DW10 engines.The application test examples in the table show that the preparative examples according to the present invention in turn are superior to Comparative Example 10.

Claims

1. 241031W00153Claims1. Use of a reaction product from the reaction of- 1 equivalent of at least one oligoalkyleneamine (B) with- from 1 to 2 equivalents of at least one Cs-Cioo-alkenyl-substituted succinic acid derivative (A) selected from the group consisting of- the anhydride,- the di-Ci-C4-alkyl ester, preferably methyl or ethyl ester, and- the dicarboxylic acidand subsequent reaction with- at least 1 equivalent of at least one dicarboxylic acid derivative (C) which is different from compound (A) and is selected from the group consisting of- the anhydride- the di-Ci-C4-alkyl ester, preferably methyl or ethyl ester, and- the dicarboxylic acidas a detergent additive for diesel fuels.

2. Use according to claim 1, characterised in that the Cs-Cioo-alkenyl-substituted succinic acid is selected from the group consisting of- dodecenyl succinic acid,- hexadecenyl succinic acid,- eicosenyl succinic acid, and- polyisobutenyl-substituted succinic acid, wherein the polyisobutenyl radical has a number average molecular weight Mn of from 500 to 1400, preferably from 550 to 1300.

3. Use according to any one of the preceding claims, characterised in that the oligoalkyleneamine (B) is selected from the group consisting of- diethylenetriamine,- triethylenetetraamine,- tetraethylenepentaamine- pentaethylenehexaamine and- tripropylenetetraamine.

4. Use according to one of the preceding claims, characterised in that the stoichiometric ratio of (A) : (B) is about241031W001545. Use according to one of the preceding claims, characterised in that dicarboxylic acid (C) is a 1,4- dicarboxylic acid.

6. Use according to claim 5, characterised in that the 1 ,4-dicarboxylic acid is selected from the group consisting of- succinic acid,- Cs-Cioo-alkenyl-substituted succinic acid,- maleic acid and- phthalic acid.

7. Use according to one of the preceding claims, characterised in that dicarboxylic acid (C) is maleic acid or succinic acid or a derivative thereof.

8. Use according to any one of the preceding claims, characterised in that the reaction product comprises the compound according to the general formulawhereinR1is a Cs-Gwo-alkeny I radical,R2is 1 ,2-ethylene, 1- or 2-C8-Cioo-alkenyl-substituted 1 ,2-ethylene or 1 ,2-vinylidene andx is a positive integer 1, 2, 3 or 4.241031W001559. Use according to one of claims 1 to 7, characterised in that the reaction is carried out in addition to the dicarboxylic acid derivative (C) with at least 1 equivalent of (D) at least one derivative of the optionally substituted salicylic acid or the optionally substituted anthranilic acid, preferably the C1-C4 alkyl ester or the carboxylic acid, particularly preferably the methyl or ethyl ester.

10. Use according to Claim 9, characterised in that the reaction product comprises the compound according to the general formulaR1is a Cs-Cwo-alkeny I radical,R2is 1 ,2-ethylene, 1- or 2-C8-Cioo-alkenyl-substituted 1 ,2-ethylene or 1 ,2-vinylidene,x is a positive integer 1, 2, 3 or 4,R3is hydrogen, Ci- to C2o-alky I or Ci- to C2o-alky loxy , andX is -OH or -NH2.

11. Use according to one of the preceding claims, characterised in that the reaction product has an acid number of from 50 to 150 mg KOH / g, preferably from 60 to 140, more preferably from 70 to 130, even more preferably from 80 to 130, and especially from 90 to 120 mg KOH / g, wherein the acid number is determined via potentiometric titration at 20 °C in toluene / ethanol 2:1 (v / v) using 0,1 N (0,1 mol / l) KOH in ethanol.241031W0015612. Use according to one of the preceding claims as an additive for reducing or preventing deposits in injection systems of direct-injection diesel engines, in particular in common-rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, in particular of diesel engines with common-rail injection systems, and / or for minimising the power loss in direct-injection diesel engines, in particular in diesel engines with common-rail injection systems.

13. Use according to claim 12 as an additive for reducing or preventing deposits Internal Diesel Injector Deposits (IDID).

14. Use according to claim 12 as an additive for reducing or preventing deposits as measured according to the DW 10 C-test method and optionally according to the XUD9- and / or DW 10 B- test method.

15. Use according to one of the claims 1 to 11 as an additive for reducing or suppressing the formation of at least one of inlet valve deposits (or intake valve deposits), exhaust valve deposits, combustion chamber deposits, piston top deposits (or piston crown deposits), cylinder head deposits, and injector nozzle fouling, reducing or suppressing or influencing particulate formation in the exhaust gas, reducing or suppressing or removing deposit formation within the exhaust gas recirculation system or the exhaust system, especially in exhaust gas aftertreatment devices such as exhaust gas catalysts and diesel particulate filters.

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