Fuel composition for spark-ignition internal combustion engine

Abstract

The present invention relates to an additive package for a methanol-containing fuel composition for a spark-ignited internal combustion engine, their use and a method for operating a spark-ignited internal combustion engine using such a fuel composition.

Description

TECHNICAL FIELD

[0001] The present invention relates to additive packages for methanol-containing fuel compositions for spark-ignition internal combustion engines, their use, and a method of operating a spark-ignition internal combustion engine using such a fuel composition. BACKGROUND OF THE INVENTION

[0002] For environmental protection reasons and to use sustainable fuel sources, gasoline fuel compositions typically contain alcohols. Methanol and ethanol are commonly used as alcohols, but higher alcohols such as butanol can also be used.

[0003] The use of alcohols in gasoline presents some disadvantages. On the one hand, due to the increased hydrophilicity of alcohols, seals tend to swell and, in particular, ferrous materials are subject to enhanced corrosion. On the other hand, the effect on fuel additives is that, due to the changed hydrophilicity of the fuel, additive packages optimized for conventional fuels must be reconfigured to avoid incompatibilities, insolubilities, and miscibility gaps.

[0004] Gasoline-ethanol blends (such as E10) have been around for many years. Currently, the increasing use of methanol makes it necessary to develop additive packages for methanol-containing fuels. SUMMARY OF THE INVENTION

[0005] An object of the present invention is to provide an additive package for methanol-containing fuels.

[0006] Due to its lower hydrophobicity, methanol fuel reduces the solubility of the typical components of the additive package in the resulting fuel. Therefore, even additive packages established for ethanol-containing fuels cannot simply be transferred to methanol-containing fuels but need to be adjusted.

[0007] Specifically, the highly hydrophobic components in the additive package, in particular polyisobutenylamine or polyisobutene-substituted Mannich compounds, are greatly affected by this reduced solubility, and thus the components of the additive package and the methanol content need to be adjusted.

[0008] The additive package according to the invention shows a lower tendency to turbidity in the fuel and exhibits high stability during storage, especially at low temperatures.

[0009] Accordingly, an object of the present invention is a fuel composition for a spark-ignition internal combustion engine, the fuel composition comprising a major amount of fuel selected from:

[0010] - 97 wt% to 0 wt% gasoline and

[0011] - 3 wt% to 100 wt% methanol

[0012] The fuel composition comprises a minor amount of at least one fuel additive package, the at least one fuel additive package comprising:

[0013] -At least one sediment control agent (A) selected from the group consisting of:

[0014] --(A1) Polyalkyleneamine

[0015] --(A2) Quaternary ammonium compound

[0016] --(A3) Polyetheramine

[0017] --(A4) Polyisobutylene-substituted Mannich compound

[0018] --(A5) Polyalkenyl succinimide

[0019] --(A6) Branched amine

[0020] -At least one corrosion inhibitor (B) selected from the group consisting of:

[0021] --(B1) Hydrolyzed copolymer of olefin and carboxylic acid

[0022] --(B2) Dimer fatty acid

[0023] --Amide of aliphatic or aromatic carboxylic acid and primary or secondary amine with at least one additional functional group selected from the group consisting of carboxylic acid group, sulfonic acid group and amino group,

[0024] -At least one carrier oil (C) selected from the group consisting of:

[0025] --Polyolefin,

[0026] --Polyester,

[0027] --Polyalkoxylate,

[0028] --Aliphatic polyether,

[0029] --Aliphatic polyetheramine,

[0030] --Alkylphenol-initiated polyether,

[0031] --Alkylphenol-initiated polyetheramine, and

[0032] --Carboxylic acid ester of long-chain alkanol,

[0033] -At least one turbidity remover (D) selected from the group consisting of:

[0034] --Alkyl-substituted phenolsulfonate and naphthalenesulfonate,

[0035] --Fatty acid,

[0036] --Alcohol alkoxylate

[0037] -- Phenols, alkylphenols and their alkoxylates,

[0038] -- Phenolic resins and alkylphenolic resins,

[0039] -- Condensation products of ethylene oxide (EO) and propylene oxide (PO),

[0040] -- Polyethyleneimine,

[0041] -- Alkoxylated polyethyleneimine, and

[0042] -- Polysiloxanes,

[0043] - At least one friction modifier (F) selected from the group consisting of:

[0044] -- (F1) The propoxylated and / or butoxylated reaction product of (a) one or more fatty acids and (b) dialkanolamine,

[0045] -- (F2) The amide of polyalkyleneamine and carboxylic acid,

[0046] -- (F3) At least one aliphatic monocarboxylic acid having 12 to 30 carbon atoms,

[0047] -- (F4) The reaction product of (a) one or more fatty acids and (b) dialkanolamine, and

[0048] -- (F5) A mixture of the following components:

[0049] --- (F5a) An aliphatic saturated or unsaturated monocarboxylic acid having 12 to 24 carbon atoms or its dimer or trimer product, which may exist as a free carboxylic acid and / or in the form of an ammonium salt, amide, ester and / or nitrile, and

[0050] --- (F5b) A polycyclic hydrocarbon compound, which can be obtained from the distillation residue of natural oil that has been extracted from tree resins. Description of the Drawings

[0051] Figure 1 Shows an embodiment of the present invention, in which KEROCOM PIBA 03 (CAS No. 886464-29-5, commercially available from BASF SE, Ludwigshafen, having an amine value of 22 to 27 mg KOH / g, a 65 wt% solution in hydrocarbon) is added to a gasoline fuel containing 85 vol% ethanol (E85).

[0052] Figure 2An embodiment of the present invention is shown, in which KEROCOM PIBA 03 (CAS No. 886464-29-5, commercially available from BASF SE, Ludwigshafen, having an amine value of 22 to 27 mg KOH / g, a 65 wt% solution in hydrocarbon) is added to a gasoline fuel containing 85 vol% methanol (M85). Detailed Description of the Invention

[0053] The compounds of the fuel are described in more detail as follows:

[0054] Gasoline

[0055] In the context of the present invention, gasoline fuel refers to a liquid hydrocarbon fraction fuel with a boiling point within the gasoline range. It is in principle applicable to all types of gasoline, including "light" and "heavy" gasoline grades. The gasoline fuel may also contain a certain amount of other fuels, such as ethanol for example.

[0056] Generally, the gasoline fuel that can be used according to the present invention may additionally exhibit one or more of the following characteristics:

[0057] The aromatic compound content of the gasoline fuel is preferably not more than 50 vol%, and more preferably not more than 35 vol%. The preferred range of the aromatic compound content is 1 vol% to 45 vol%, especially 5 vol% to 35 vol%.

[0058] The sulfur content of the gasoline fuel is preferably not more than 100 wt ppm, and more preferably not more than 10 wt ppm. The preferred range of the sulfur content is 0.5 wt ppm to 150 wt ppm, especially 1 wt ppm to 10 wt ppm.

[0059] The olefin content of the gasoline fuel does not exceed 21 vol%, preferably does not exceed 18 vol%, and more preferably does not exceed 10 vol%. The preferred range of the olefin content is 0.1 vol% to 21 vol%, especially 2 vol% to 18 vol%.

[0060] The benzene content of the gasoline fuel does not exceed 1.0 vol%, and preferably does not exceed 0.9 vol%. The preferred range of the benzene content is 0 vol% to 1.0 vol%, especially 0.05 vol% to 0.9 vol%.

[0061] The oxygen content of the gasoline fuel does not exceed 45 wt%, preferably 0 wt% to 45 wt%, and most preferably 0.1 wt% to 3.7 wt% (type I) or most preferably 3.7 wt% to 45 wt% (type II).

[0062] The summer vapor pressure of the gasoline fuel generally does not exceed 70 kPa, and preferably does not exceed 60 kPa (at 37 °C).

[0063] The research octane number (“RON”) of the gasoline fuel is typically from 90 to 100. The corresponding motor octane number (“MON”) typically ranges from 80 to 90.

[0064] The above characteristics are determined by conventional methods (DIN EN 228).

[0065] Methanol

[0066] The methanol used in the fuel composition can be of fossil origin or from renewable resources or a mixture thereof, preferably from renewable resources.

[0067] Fossil-based methanol is mainly obtained by the hydrogenation of carbon monoxide, usually on an industrial scale from syngas (a mixture of hydrogen and carbon monoxide). To utilize the stoichiometric excess of hydrogen in the syngas, carbon dioxide is usually also fed into the reaction mixture.

[0068] Methanol can also be obtained from the hydrogenation of carbon dioxide, for example from the hydrogenation of carbon dioxide captured from flue gases (carbon capture and utilization, CCU). Whether this is of fossil or renewable origin depends on the sources of the carbon dioxide and hydrogen used in this process.

[0069] In a preferred embodiment, as described in WO 2023 / 213583, which is incorporated herein by reference, methanol is produced by reacting hydrogen with carbon dioxide using deuterium-depleted hydrogen. The methanol thus obtained is characterized by a deuterium content of less than 90 ppm (based on the total hydrogen content).

[0070] Methanol from renewable resources is preferably obtained from the fermentation of carbohydrate-containing substrates in the presence of microorganisms and / or enzymes.

[0071] Suitable carbohydrate-containing substrates are monomeric or polymeric sugars such as starch, lignin, cellulose, and hemicellulose.

[0072] As used herein, the terms “renewable” or “bio-based” with respect to a material or compound mean a material or compound obtained from a “new carbon” source, as measured by ASTM test method D 6866, “Determining the Biobased Content of Natural Range Materials Using Radio-carbon and Isotope Ratio Mass Spectrometry Analysis”. This test method measures the 14 C / 12 C isotope ratio and compare it with that in a standard 100% bio-based material, thereby obtaining the percentage of the bio-based content of the sample. 14 C / 12 C isotope ratio to obtain the percentage of the bio-based content of the sample.

[0073] "Renewable" or "bio-based" compounds can be prepared from biomass using thermochemical methods (e.g., Fischer-Tropsch catalysts), biocatalysts (e.g., fermentation), or other methods. The assessment of the renewable-based carbon content of materials can be carried out by standard test methods, such as using radiocarbon and isotope ratio mass spectrometry. ASTM International (formerly known as the American Society for Testing and Materials) has established standard methods for assessing the bio-based content of materials. This ASTM method is named ASTM-D6866. Applying ASTM-D6866 to derive the "bio-based content" is based on the same concept as radiocarbon dating but does not use the age equation. This analysis is carried out by deriving the ratio of the amount of radiocarbon ( 14 C) in an unknown sample to the amount of a modern reference standard. This ratio is reported as a percentage and has the unit "pMC" (percent modern carbon). If the material being analyzed is a mixture of modern radiocarbon and fossil carbon (containing very low levels of radiocarbon), the pMC value obtained is directly related to the amount of biomass material present in the sample.

[0074] "Bio-based materials" are organic materials in which the carbon comes from CO2 present in the atmosphere that was recently (on a human time scale) fixed using solar energy (photosynthesis). On land, this CO2 is captured or fixed by plant life (e.g., crops or forestry materials). In the ocean, this CO2 is captured or fixed by photosynthetic bacteria or phytoplankton. For example, bio-based materials have a 14 C / 12 C isotope ratio greater than 0.

[0075] In contrast, fossil-based materials have a 14 C / 12 C isotope ratio of approximately 0. A small fraction of the carbon atoms in atmospheric carbon dioxide are the radioactive isotope 14 C, which is produced when atmospheric nitrogen is struck by neutrons generated by cosmic rays, causing the nitrogen to lose a proton and form carbon with an atomic mass of 14 ( 14 C), which is then immediately oxidized to carbon dioxide. A small but measurable fraction of atmospheric carbon is in the form of 14in the form of CO2. In a process called photosynthesis, green plants process atmospheric carbon dioxide into organic molecules. Virtually all forms of life on Earth depend on this production of organic molecules by green plants to generate the chemical energy that promotes growth and reproduction. Thus, the 14 C formed in the atmosphere ultimately becomes part of all life forms and their biological products, enriching biomass and the organisms that feed on biomass with 14 C. In contrast, carbon from fossil fuels does not have the characteristics of renewable organic molecules derived from atmospheric carbon dioxide 14 C: 12 C ratio.

[0076] In a preferred embodiment of the present invention, the biobased content of the methanol used in the fuel is greater than 0 (zero), preferably at least 10%, more preferably at least 20%, even more preferably at least 40%, and especially at least 60%.

[0077] The additive package is suitable for a fuel composition comprising:

[0078] - 97 vol% to 0 vol% gasoline, preferably 95 vol% to 5 vol%, more preferably 92.5 vol% to 10 vol%, even more preferably 90 vol% to 15 vol%, and especially 85 vol% to 20 vol%, and

[0079] - 3 vol% to 100 vol% methanol, preferably 5 vol% to 95 vol%, more preferably 7.5 vol% to 90 vol%, even more preferably 10 vol% to 85 vol%, and especially 15 vol% to 80 vol%.

[0080] Preferred embodiments of the methanol content of the fuel are

[0081] M5: 5 vol% methanol and 95 vol% gasoline,

[0082] M10: 10 vol% methanol and 90 vol% gasoline,

[0083] M15: 15 vol% methanol and 85 vol% gasoline,

[0084] M85: 85 vol% methanol and 15 vol% gasoline,

[0085] M100: 100 vol% methanol.

[0086] The additive package for a methanol - gasoline composition according to the present invention preferably comprises

[0087] - at least one deposit control agent (A),

[0088] - at least one corrosion inhibitor (B),

[0089] - at least one carrier oil (C),

[0090] - at least one turbidity remover (D) selected from the group consisting of:

[0091] -- (D1) alkoxylated polyethyleneimine,

[0092] -- (D2) alkylphenol resin and

[0093] -- (D3) alkyl-, aryl- or alkylaryl sulfonate or sulfate

[0094] - at least one friction modifier (F).

[0095] At least one deposit control agent (A) is selected from the group consisting of:

[0096] - (A1) polyalkyleneamine,

[0097] - (A2) quaternary ammonium compound,

[0098] - (A3) polyetheramine,

[0099] - (A4) polyisobutylene-substituted Mannich compound,

[0100] - (A5) polyalkenyl succinimide, and

[0101] - (A6) branched amine.

[0102] (A1) Polyalkyleneamine

[0103] Polyalkyleneamine R 6 -NH2 is an amine with a hydrocarbon residue derived from the polymerization of at least one olefin.

[0104] Residue R 6 is a hydrocarbon residue containing 12 to 200, preferably 16 to 150, more preferably 20 to 100, even more preferably 30 to 90 and especially 40 to 80 carbon atoms, which can be obtained by the polymerization of olefins, preferably by the polymerization of an olefin mixture containing propylene, 1-butene or isobutene, more preferably by propylene or isobutene, and most preferably by isobutene.

[0105] In one embodiment of the present invention, the polyolefin from which the residue R 6 is based is derived from an olefin polymer. The olefin polymer may include homopolymers and copolymers of polymerizable olefin monomers having 2 to about 16 carbon atoms, 2 to about 6 carbon atoms or 2 to about 4 carbon atoms.

[0106] Copolymers are those in which two or more olefin monomers are copolymerized by known conventional methods to obtain polyolefins having units derived from each of the two or more olefin monomers within their structure. Thus, "copolymers" include copolymers, terpolymers, and tetrapolymers.

[0107] The "polyalkene" from which the polyolefin-substituted amine is derived is also commonly referred to as "polyolefin" conventionally.

[0108] The olefin monomers from which the olefin polymers are derived are polymerizable olefin monomers having one or more ethylenically unsaturated groups (i.e., >C═C<); in other words, they are monoolefin monomers such as ethylene, propylene, 1-butene, isobutene (2-methyl-1-butene), 1-octene, or polyolefin monomers (usually diolefin monomers) such as 1,3-butadiene and isoprene.

[0109] Olefin monomers are usually polymerizable terminal olefins, i.e., olefins having a >C═CH2 group in their structure. However, polymerizable internal olefin monomers characterized by a group of the formula >C—C═C—C< can also be used.

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

[0111] In another embodiment, olefin polymers can be prepared by polymerizing a C4 refinery stream having a butene content of about 35 wt% to about 75 wt% and an isobutene content of about 30 wt% to about 60 wt% in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes typically mainly (more than about 80% of all repeating units) contain repeating isobutene units of the type (—CH2—C(CH3)2—).

[0112] In another embodiment, the polyolefin substituent of the polyolefin-substituted amine is derived from polyisobutene.

[0113] In a preferred embodiment, the amine R 6 —NH2 can be obtained by polymerization of the above-mentioned olefins, followed by hydroformylation and reductive amination (preferably with ammonia).

[0114] Such processes for preparing polyolefin-substituted amines, which involve the reaction of a hydroformylated olefin with a polyamine and hydrogenation of the reaction product, are described in US Pat. Nos. 5,567,845 and 5,496,383.

[0115] Another process for preparing polyolefin-substituted amines involves the hydroformylation of polybutene or polyisobutylene in the presence of CO and hydrogen over a catalyst such as rhodium or cobalt at elevated pressure and temperature as described in US Pat. No. 4,832,702.

[0116] In another but less preferred embodiment, the amine R 6 -NH2 can be obtained by a process in which polyisobutene with a high double bond content is reacted with nitrogen oxides or a mixture of nitrogen oxides and oxygen (WO 96 / 03367A1). Subsequent elimination and hydrogenation produce polyisobuteneamines containing one less carbon atom than the polyisobuteneamines according to the aforementioned production process, since the hydroformylation step is omitted.

[0117] Another method for preparing polyolefin-substituted amines involves converting the polyolefin to the corresponding epoxide with the aid of a conventional epoxidation reagent with or without a catalyst, and converting the epoxide to the polyolefin-substituted amine by reaction with ammonia or an amine under reductive amination conditions, as described in US Pat. No. 5,350,429.

[0118] Methods for preparing polyolefin-substituted amines include reacting halogenated olefin polymers with amines as described in U.S. Patents 3,275,554, 3,438,757, 3,454,555, 3,565,804, 3,755,433, and 3,822,289.

[0119] Another method for preparing polyolefin-substituted amines involves the hydrogenation of β-amino nitriles which have been prepared by the reaction of amines with nitriles, as described in US Pat. No. 5,492,641.

[0120] Preferably, in the amine R 6 -NH2, residue R 6 Derived from polyisobutylene having a number average molecular weight Mn of 168 to 2300, more preferably 224 to 1500, even more preferably 550 to 1300, most preferably 700 to 1300 and especially 950 to 1050.

[0121] In a preferred embodiment, these amines are obtainable by oligomerization of propene, isobutene, 1-butene or 2-butene, preferably propene or isobutene, in particular isobutene, to form oligomer mixtures or polymers containing double bonds, followed by hydroformylation and reductive amination with ammonia.

[0122] Preferably, the oligomers or polymers containing isobutene in copolymerized form have a high content of terminal olefinic double bonds (α-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%.

[0123] To prepare such oligomers or polymers containing isobutene in copolymerized form, suitable sources of isobutene are pure isobutene or C4 hydrocarbon streams containing isobutene, such as C4 raffinate, especially "raffinate 1", C4 fractions from isobutane dehydrogenation, C4 fractions from steam crackers and from FCC crackers (fluid catalytic cracking), provided that they are substantially free of 1,3-butadiene present therein. The C4 hydrocarbon stream from an FCC refining unit is also referred to as a "b / b" stream. Also suitable C4 hydrocarbon streams containing isobutene are, for example, the product streams from the co-oxidation of propylene-isobutane or the product streams from a metathesis unit, which are usually used after conventional purification and / or concentration. Suitable C4 hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm of butadiene. The presence of 1-butene and cis- and trans-2-butene is substantially immaterial. Generally, the isobutene concentration in the C4 hydrocarbon stream is in the range of 40 wt% to 60 wt%. For example, raffinate 1 generally consists essentially of 30 wt% to 50 wt% isobutene, 10 wt% to 50 wt% 1-butene, 10 wt% to 40 wt% cis- and trans-2-butene, and 2 wt% to 35 wt% butane; during the polymerization, the unbranched butenes in raffinate 1 are generally almost inert and only isobutene is polymerized.

[0124] In a preferred embodiment, the monomer source for the polymerization is an industrial C4 hydrocarbon stream having an isobutene content of 1 wt% to 100 wt%, especially 1 wt% to 99 wt%, particularly 1 wt% to 90 wt%, more preferably 30 wt% to 60 wt%, especially the raffinate 1 stream, the b / b stream from an FCC refining unit, the product stream from the co-oxidation of propylene-isobutane or the product stream from a metathesis unit.

[0125] Especially when the raffinate 1 stream is used as the isobutene source, it has been found useful to use water as the sole initiator or as an additional initiator, especially when the polymerization is carried out at a temperature of -20 °C to +30 °C, especially 0 °C to +20 °C. However, at a temperature of -20 °C to +30 °C, especially 0 °C to +20 °C, when using the raffinate 1 stream as the isobutene source, the use of an initiator can be omitted.

[0126] The monomer mixture containing isobutene may contain small amounts of contaminants such as water, carboxylic acids or mineral acids without any significant loss of yield or selectivity. Appropriately, these harmful substances are removed from the monomer mixture containing isobutene (e.g., by adsorption on a solid adsorbent such as activated carbon, molecular sieve or ion exchanger) to avoid the accumulation of these impurities.

[0127] Although less preferred, it is also possible to polymerize a monomer mixture of isobutene or a hydrocarbon mixture containing isobutene with an ethylenically unsaturated monomer copolymerizable with isobutene. If a monomer mixture of isobutene and a suitable comonomer is to be copolymerized, the monomer mixture contains 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 the comonomer.

[0128] Due to their high proportion of vinylidene double bonds, these polyisobutenes are particularly prone to hydroformylation and subsequent amination (preferably with ammonia) reactions to produce the corresponding polyisobutenylamines as amines R 6 -NH2, which represents a preferred embodiment of the present invention.

[0129] Such polyisobutenylamines are commercially available under the trade name KEROCOM(R) PIBA from BASF SE, Ludwigshafen.

[0130] The idealized structure of such polyisobutenylamines is

[0131]

[0132] For a number-average molecular weight Mn of 168 to 2300 of the base polyisobutene, x is from 1 to 39; for a Mn of 224 to 1500, x is from 2 to 25; for a Mn of 550 to 1300, x is from 8 to 21; for a Mn of 700 to 1300, x is from 10 to 21; and for a Mn of 950 to 1050, x is from 15 to 17.

[0133] If the base polyisobutene is prepared from an isobutene-containing C4 hydrocarbon stream (see above) containing monomers other than isobutene, the polymer backbone contains other monomers in polymerized form, such as 1-butene and cis- and trans-2-butene, especially 1-butene.

[0134] (A2) Quaternary ammonium compound

[0135] The quaternary ammonium compound (A2) preferably has the following formula:

[0136] + NR 1 R 2R 3 R 4 A -

[0137] wherein

[0138] A - represents an anion, preferably a carboxylate R 5 COO - or a carbonate R 5 O-COO - ,

[0139] and

[0140] R 1 、R 2 、R 3 、R 4 and R 5 are each independently an organic residue having 1 to 100 carbon atoms, a substituted or unsubstituted, preferably unsubstituted, straight-chain or branched alkyl, alkenyl or hydroxyalkyl residue having 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,

[0141] R 5 may also be a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 20, preferably 5 to 12 carbon atoms.

[0142] It is also possible that the anion can carry multiple negative charges, for example if the anion of a dibasic acid is used, in which case the stoichiometric ratio of the ammonium ion to the anion corresponds to the ratio of the positive and negative charges.

[0143] The same applies to salts in which the cation carries more than one ammonium ion (for example a substituent connects two or more ammonium ions).

[0144] In the organic residue, the carbon atoms may be interspersed with one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, and may be substituted by C6-C 12 aryl, C5-C 12 cycloalkyl or a five- or six-membered oxygen-, nitrogen- and / or sulfur-containing heterocycle, or two of them together form an unsaturated, saturated or aromatic ring, which ring may be interspersed with one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, wherein said groups may each be substituted by a functional group, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocycle.

[0145] Residues R 1 to R 4Both of them in [the compound] can together form an unsaturated, saturated or aromatic ring, preferably a five-, six- or seven-membered ring (including the nitrogen atom of the ammonium ion).

[0146] In this case, the ammonium cation can be a morpholinium, piperidinium, piperazinium, pyrrolidinium, imidazolinium or pyridinium cation.

[0147] In these definitions,

[0148] C1–C which can be substituted by a functional group, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocycle 20The alkyl group 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, α,α-dimethylbenzyl, diphenylmethyl, 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-bis-(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-octoxyethyl, 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, or 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl, and

[0149] interspersed with one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C2–C 20The alkyl group is, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxoundecyl, 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-dioxoundecyl, 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-dioxoundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl.

[0150] If two groups 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-C1-C4-alkyl-1-aza-1,3-propenylene, 1,4-but-1,3-dienylene, 1-aza-1,4-but-1,3-dienylene or 2-aza-1,4-but-1,3-dienylene.

[0151] The number of oxygen and / or sulfur atoms and / or imino groups is not subject to any restriction. Generally speaking, there will be no more than 5, preferably no more than 4, and very particularly preferably no more than 3 in this group.

[0152] In addition, there is usually at least one carbon atom, preferably at least two carbon atoms, between any two heteroatoms.

[0153] The substituted and unsubstituted imino groups can be, for example, imino, methylimino, isopropylimino, n-butylimino or tert-butylimino.

[0154] In addition,

[0155] The functional group can be carboxyl, carboxamide, hydroxyl, di(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, cyano or C1-C4 alkoxy.

[0156] C6–C which may be substituted by a functional group, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocycle 12 The aryl is, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenylyl, 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,

[0157] C5–C which may be substituted by a functional group, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and / or heterocycle 12 The cycloalkyl 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,

[0158] The five- or six-membered heterocycle containing oxygen, nitrogen and / or sulfur is, for example, furyl, thienyl, pyrrolyl, pyridyl, indolyl, benzoxazolyl, dioxolanyl, dioxo, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrrolyl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthienyl, isopropylthienyl or tert-butylthienyl, and

[0159] The C1 to C4 alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

[0160] The residue R 1 to R 5 is preferably C2-C 18 alkyl or C6-C 12 aryl, more preferably C4-C 16 alkyl or C6-C 12 aryl, and even more preferably C4-C 16 alkyl or C6 aryl.

[0161] The residue R 1 to R 5 may be saturated or unsaturated, preferably saturated.

[0162] Preferred residue R 1 to R 5 does not carry any heteroatoms other than carbon with hydrogen removed.

[0163] R 1 to R 4 Preferred examples of R are 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, α,α-dimethylbenzyl, diphenylmethyl, p-tolylmethyl or 1-(p-butylphenyl)ethyl.

[0164] In a preferred embodiment, at least one of the residues R 1 to R 4 is selected from the group consisting of 2-hydroxyethyl, hydroxyprop-1-yl, hydroxyprop-2-yl, 2-hydroxybutyl or 2-hydroxy-2-phenylethyl.

[0165] In one embodiment, R 5 is a polyolefin homopolymer or copolymer, preferably a polypropylene, polybutene or polyisobutene residue, having a number average molecular weight (M n ) of 85 to 20,000, such as 113 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500 or 800 to 1,500. Preferred are polypropylene-based, polybutene-based and polyisobutene-based groups, such as having a number average molecular weight M n of 3,500 g / mol to 5,000 g / mol, 350 g / mol to 3,000 g / mol, 500 g / mol to 2,500 g / mol, 700 g / mol to 2,500 g / mol and 800 g / mol to 1,500 g / mol.

[0166] Preferred examples of the anion A - are acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, trimethylhexanoic acid, 2-propylheptanoic acid, isononanoic acid, versatic acid, capric acid, undecanoic acid, lauric acid, saturated or unsaturated fatty acids having 12 to 24 carbon atoms or mixtures thereof, salicylic acid, oxalic acid mono C1-C4 alkyl esters, phthalic acid mono C1-C4 alkyl esters, C 12 -C 100Anions of alkyl and alkenyl succinic acids, in particular dodecenyl succinic acid, hexadecenyl succinic acid, eicoseneyl succinic acid and polyisobutenyl succinic acid. Further examples are methyl carbonate, ethyl carbonate, n-butyl carbonate, 2-hydroxyethyl carbonate and 2-hydroxypropyl carbonate.

[0167] In a particularly preferred embodiment, a nitrogen-containing compound quaternized in the presence of an acid or in an acid-free manner can be obtained by adding a compound comprising at least one oxygen- or nitrogen-containing group capable of reacting with an acid anhydride and at least one further quaternizable amino group to a polycarboxylic acid anhydride compound, followed by quaternization, in particular with an epoxide such as styrene oxide or propylene oxide, in the absence of free acid, as described in WO 2012 / 004300, or with a carboxylic acid ester such as dimethyl oxalate or methyl salicylate. Suitable compounds having at least one oxygen- or nitrogen-containing group capable of reacting with an acid anhydride and at least one further quaternizable amino group are in particular polyamines having at least one primary or secondary amino group and at least one tertiary amino group, in particular N,N-dimethyl-1,3-propanediamine, N,N-dimethyl-1,2-ethanediamine or N,N,N'-trimethyl-1,2-ethanediamine. Useful polycarboxylic acid anhydrides are in particular dicarboxylic acids such as succinic acid which have relatively long-chain hydrocarbon substituents, preferably a number-average molecular weight M n of from 200 to 10,000, in particular from 350 to 5000. Such a quaternized nitrogen compound is, for example, the reaction product of polyisobutenyl succinic anhydride with 3-(dimethylamino)propylamine obtained at 40 °C, in which the polyisobutenyl group in the polyisobutenyl succinic anhydride usually has an M n of 1000, and 3-(dimethylamino)propylamine forms a polyisobutenyl succinamide and is then quaternized in the absence of free acid with dimethyl oxalate or methyl salicylate or with styrene oxide or propylene oxide.

[0168] Further quaternized nitrogen compounds suitable as compound (A2) are described in:

[0169] WO 2006 / 135881 A1, pages 5, line 13 to page 12, line 14;

[0170] WO 10 / 132259 A1, pages 3, line 28 to page 10, line 25;

[0171] WO 2008 / 060888 A2, pages 6, line 15 to page 14, line 29;

[0172] WO 2011 / 095819 A1, pages 4, line 5 to page 9, line 29;

[0173] GB 2496514 A, paragraphs

[00012] to

[00041] ;

[0174] WO 2013 / 117616 A1, page 3, line 34 to page 11, line 2;

[0175] WO 14 / 202425 A2, page 3, line 14 to page 5, line 9;

[0176] WO 14 / 195464 A1, page 15, line 31 to page 45, line 26 and page 75, lines 1 to 4;

[0177] WO 15 / 040147 A1, page 4, line 34 to page 5, line 18 and page 19, line 11 to page 50, line 10;

[0178] WO 14 / 064151 A1, page 5, line 14 to page 6, line 17 and page 16, line 10 to page 18, line 12;

[0179] WO 2013 / 064689 A1, page 18, line 16 to page 29, line 8; and

[0180] WO 2013 / 087701 A1, page 13, line 25 to page 19, line 30,

[0181] WO 13 / 000997 A1, page 17, line 4 to page 25, line 3,

[0182] 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,

[0183] These documents are each incorporated herein by reference.

[0184] In one embodiment, the quaternary ammonium compound (A2) has the following formula:

[0185]

[0186] wherein in this formula,

[0187] PIB represents a polyisobutenyl residue having a number average molecular weight M n of 550 g / mol to 2300 g / mol, preferably 650 g / mol to 1500 g / mol and more preferably 750 g / mol to 1300 g / mol,

[0188] R represents a C1 to C4 alkyl or hydroxy-C1 to C4 alkyl, preferably methyl or 2-hydroxypropyl, and

[0189] A - represents an anion, preferably a carboxylate R as defined above 5 COO - or a carbonate R 5 O-COO - , more preferably acetate, salicylate or methyl oxalate.

[0190] In another preferred embodiment, the quaternary ammonium compound (A2) has the following formula:

[0191]

[0192] wherein in this formula,

[0193] PIB represents a polyisobutenyl residue having a number average molecular weight M n of 550 g / mol to 2300 g / mol, preferably 650 g / mol to 1500 g / mol and more preferably 750 g / mol to 1300 g / mol,

[0194] R represents a hydroxy-C1 to C4 alkyl group, preferably 2-hydroxypropyl.

[0195] In another embodiment, the quaternized compound (A2) has the following formula:

[0196]

[0197] wherein in this formula,

[0198] PIB represents a polyisobutenyl residue having a number average molecular weight M n of 550 g / mol to 2300 g / mol, preferably 650 g / mol to 1500 g / mol and more preferably 750 g / mol to 1300 g / mol,

[0199] R represents a C1 to C4 alkyl group or a hydroxy-C1 to C4 alkyl group, preferably methyl, and

[0200] A - represents an anion, preferably a carboxylate R as defined above 5 COO - or a carbonate R 5 O-COO - , more preferably salicylate or methyl oxalate.

[0201] In another embodiment, the quaternary ammonium compound (A2) has the following formula:

[0202]

[0203] wherein in this formula,

[0204] R a represents C1–C 20 alkyl, preferably C9 to C 17 alkyl, more preferably undecyl, tridecyl, pentadecyl or heptadecyl,

[0205] R b represents hydroxy-C1 to C4 alkyl, preferably 2-hydroxypropyl or 2-hydroxybutyl, and

[0206] A - represents an anion, preferably carboxylate R as defined above 5 COO - and more preferably R 5 COO - is the carboxylate of a fatty acid, especially A - is acetate, 2-ethylhexanoate, oleate or polyisobutenyl succinate.

[0207] In one embodiment, the quaternary ammonium compound (A2) has the following formula:

[0208]

[0209] wherein in this formula,

[0210] For X where i = 1 to n and 1 to m iEach is independently 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-

[0211] m and n are each independently a positive integer, provided 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

[0212] R represents a C1 to C4 alkyl group, preferably methyl, and

[0213] A - represents an anion, preferably a carboxylate R as defined above 5 COO - or a carbonate R 5 O-COO - and more preferably salicylate or methyl oxalate

[0214] In another preferred embodiment, the quaternary ammonium compound (A2) has the following formula:

[0215]

[0216] wherein in this formula,

[0217] R a and R b each independently represent a C1–C 20 alkyl group or a hydroxy-C1 to C4 alkyl group, preferably R a represents a C1–C20 An alkyl group, preferably ethyl, n-butyl, n-octyl, n-dodecyl, tetradecyl or hexadecyl, and R b represents a hydroxy-C1 to C4 alkyl group, preferably 2-hydroxypropyl,

[0218] A - represents an anion, preferably a carboxylate R as defined above 5 COO - or a carbonate R 5 O-COO - , more preferably C 12 -C 100 alkyl and alkenyl succinic acids, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicoseneyl succinic acid and polyisobutenyl succinic acid.

[0219] (A3) Polyetheramine

[0220] Polyetheramines are alkoxylated alkanols in which the hydroxy group is converted to an amino group by amination (preferably with ammonia).

[0221] The base alkanol can be a C1 to C 30 alkanol, preferably a C2 to C 20 alkanol, more preferably a C4 to C 17 alkanol, even more preferably a C8 to C 17 alkanol, very particularly a C 13 or a C 17 alkanol, which can be straight-chain or branched, preferably branched.

[0222] Examples of alkanols are hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol and their structural and positional isomers.

[0223] In one embodiment of the invention, the alkoxylation can be started with water instead of an alkanol.

[0224] In another embodiment of the invention, the alkoxylation can be started with an alkyl-substituted phenol instead of an alkanol.

[0225] The base alkyl-substituted phenol preferably has the following formula:

[0226] R 19 -C6H4-OH

[0227] wherein

[0228] R 19 is a straight-chain or branched alkyl group having 8 to 22, preferably 9 to 17, more preferably 10 to 13 carbon atoms.

[0229] The alkyl group R 19 can be in the ortho or para position of the phenolic hydroxyl group, preferably in the para position.

[0230] The alkoxylation can be carried out with C2 to C8 alkylene oxides, which are preferably selected from the group consisting of ethylene oxide, propylene oxide, 1-butylene oxide, and 2-butylene oxide, more preferably propylene oxide and / or 1-butylene oxide.

[0231] The amination can be carried out with ammonia, C1 to C4 alkylamines, di-(C1 to C4) alkylamines, or polyethyleneimine, preferably with ammonia, methylamine, ethylamine, n-butylamine, dimethylamine, diethylamine, di(n-butyl)amine, 1,3-propanediamine, 3-(N,N-dimethylamino)propanediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine, more preferably ammonia, dimethylamine, diethylenetriamine, or triethylenetetramine, and especially ammonia.

[0232] The general formula of such preferred polyetheramines is

[0233] R 20 -O-[-X i -] n -NR 21 R 22

[0234] wherein

[0235] R 20 is hydrogen or a C1 to C 30 alkyl group, preferably a C2 to C 20 alkyl group, more preferably a C4 to C 17 alkyl group, even more preferably a C8 to C 17 alkyl group, and especially a C 13 or a C 17 alkyl group, which can be straight-chain or branched, preferably branched, or an alkyl-substituted phenyl residue R 19 -C6H4-, wherein

[0236] R 19 is a straight-chain or branched alkyl group having 8 to 22, preferably 9 to 17, more preferably 10 to 13 carbon atoms,

[0237] R 21 and R 22 are independently of each other hydrogen, a C1 to C4 alkyl group, an N,N-bis(C1 to C4 alkylamino)-C1 to C4 alkyl group, or –[-CH2-CH2-NH-] m -H,

[0238] n is from 10 to 40, preferably from 12 to 30, more preferably from 18 to 25, even more preferably from 20 to 23, m is from 1 to 4, preferably from 1 to 3, more preferably 2 or 3, and

[0239] for X where i = 1 to n i is independently 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-, and most preferably selected from the group consisting of -CH2-CH2-O-, -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-, and in particular selected from the group consisting of -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-.

[0240] In a preferred embodiment of the present invention, the group R 21 and R 22 are both hydrogen, or one of these groups is hydrogen and the other is 2-aminoethyl, 3-aminopropyl or 3-(N,N-dimethylamino)propyl. The last-mentioned groups are derived from the following diamines: 1,2-ethylenediamine, 1,3-propanediamine and 3-(N,N-dimethylamino)propylamine respectively.

[0241] The polyetheramine is advantageously prepared as described in EP-A 310 875 by reacting an alcohol of the formula R 20 -OH with propylene oxide and / or butylene oxide and then aminating with ammonia or an amine of the formula NHR 21 R 23 .

[0242] (A4) Polyisobutylene-substituted Mannich compound

[0243] Exemplary Mannich adducts are described in US 8449630 B2, and preferably the Mannich adduct of formula I according to US 8449630 B2, which is incorporated herein by reference.

[0244] In a preferred embodiment, the Mannich adduct can be obtained as described in US 8449630 B2, column 7, lines 35 to column 9, line 52.

[0245] Preferably, the Mannich adduct can be obtained by the reaction of:

[0246] - at least one hydrocarbyl-substituted phenol, preferably the phenol of formula V according to US 8449630 B2, more preferably p-hydrocarbyl-substituted phenol or p-hydrocarbyl-substituted o-cresol, with

[0247] - at least one aldehyde, preferably acetaldehyde or formaldehyde, more preferably formaldehyde, and

[0248] -At least one amine according to variant 2 of US 8449630 B2, preferably selected from the group consisting of: octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, cyclooctylamine, cyclodecylamine, di-n-butylamine, diisobutylamine, di-tert-butylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, di(2-ethylhexyl)amine, 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-dimethylpropyl-1,3-diamine, N,N-diethylpropyl-1,3-diamine, N,N-dipropylpropyl-1,3-diamine, N,N-diethylbutyl-1,4-diamine, N,N-dipropylbutyl-1,4-diamine, N,N-dimethylpentyl-1,3-diamine, N,N-diethylpentyl-1,5-diamine, N,N-dipropylpentyl-1,5-diamine, N,N-dimethylhexyl-1,6-diamine, N,N-diethylhexyl-1,6-diamine, N,N-dipropylhexyl-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, tris[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,

[0249] More preferably, it is selected from the group consisting of: dimethylamine, diethylamine, di-n-butylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N,N-dimethylpropyl-1,3-diamine, and N,N-diethylpropyl-1,3-diamine.

[0250] The hydrocarbon residue of at least one hydrocarbyl-substituted phenol preferably has a number-average molecular weight Mn of from 85 to 5000, preferably from 113 to 2500, more preferably from 550 to 1500, and especially from 750 to 1100.

[0251] In a preferred embodiment, the hydrocarbon residue is a polyisobutylene group having the aforementioned molecular weight, more preferably derived from a "reactive" polyisobutylene group as defined in US 8449630 B2.

[0252] In a preferred embodiment, the Mannich adduct has the following formula:

[0253]

[0254] Or has the following formula:

[0255]

[0256] Where

[0257] R 30 Is a hydrocarbon residue having a number-average molecular weight Mn of from 85 to 5000, preferably from 113 to 2500, more preferably from 550 to 1500, and most preferably from 750 to 1100, and especially a polyisobutylene group of the aforementioned molecular weight, more preferably derived from a "reactive" polyisobutylene group,

[0258] R 31 Is hydrogen, methyl, ethyl, isopropyl, n-butyl, tert-butyl, but-2-yl or pentyl, preferably hydrogen or methyl, and more preferably methyl, or the group -CH2-NR 32 R 33 Or the group -CH2-NH-R 34 -NR 32 R 33 ,

[0259] R 32 And R 33 Are independently of each other C1 to C6 alkyl groups, preferably C1 to C4 alkyl groups, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, even more preferably methyl, ethyl or n-butyl, or R 32 And R33 forms a five- or six-membered ring together with a nitrogen atom, preferably a pyrrolidine, piperidine or morpholine ring, and

[0260] R 34 is a divalent alkylene residue having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably selected from the group consisting of methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene and 1,6-hexylene, and especially 1,2-ethylene or 1,3-propylene.

[0261] (A5) Polyalkenyl succinimide

[0262] Compound (A5) is at least one polyalkenyl succinimide which is the reaction product of (1) a reaction intermediate that yields a hydrocarbyl dicarboxylic acid and (2) a nucleophilic reactant.

[0263] Reaction intermediate for producing hydrocarbon dicarboxylic acid (1)

[0264] Reaction intermediate (1) generally comprises the reaction product of: (a) a polyolefin containing C2 to C 18 olefin units and having a number average molecular weight (M n ) of about 500 g / mol to 5,000 g / mol, and (b) a C4 to C 10 monounsaturated acid reactant. The polyolefin (a) and the monounsaturated acid reactant (b) can react via various reaction mechanisms under various conditions to form reaction intermediate (1).

[0265] For example, reaction intermediate (1) can be formed by heating a mixture of polyolefin (a) and monounsaturated acid reactant (b) via an "ene" reaction. In this "ene" reaction, the polyolefin (a) undergoes addition of the monounsaturated acid reactant (b) at the double bond. Alternatively, the polyolefin (a) can first be halogenated, for example chlorinated or brominated with 1 wt% to 8 wt%, alternatively 3 wt% to 7 wt% of chlorine or bromine gas based on the weight of the polyolefin (a). The halogenated polyolefin is formed by passing chlorine or bromine gas through the polyolefin (a) at a temperature of 60 to 160 °C, alternatively 110 to 130 °C for 0.5 to 10 hours, alternatively 1 to 7 hours. Then the halogenated polyolefin is reacted with a C4 to C 10 monounsaturated acid reactant (b) at a temperature of 100 to 250 °C, alternatively 180 to 235 °C for 0.5 to 10 hours, alternatively 3 to 8 hours to form reaction intermediate (1).

[0266] The reaction intermediate (1) for producing a hydrocarbyl dicarboxylic acid usually contains a polyolefin substituted by the portion that produces the dicarboxylic acid. Specifically, the reaction intermediate (1) is usually an acid, anhydride, or ester containing a long-chain hydrocarbon derived from polyolefin (a), and usually per mol of polyolefin (a), it is on average 0.5 mol to 10.0 mol, alternatively 0.5 mol to 5 mol, alternatively 1.2 mol to 2.0 mol, alternatively 1.3 mol to 1.8 mol, alternatively 1.4 mol to 1.7 mol of C4 to C 10 substituted by the monounsaturated acid reactant (b) (i.e., the portion that produces the dicarboxylic acid). In one embodiment, the reaction intermediate (1) is a polyalkenyl succinic anhydride, such as polyisobutenyl succinic anhydride. These functionality ratios of the portion that produces the dicarboxylic acid to the polyolefin (such as 1.2 to 2.0, etc.) are based on the total amount of polyolefin (a) present in the resulting product formed in the above reaction.

[0267] Polyolefin (a)

[0268] The polyolefin (a) of the present disclosure contains C2 to C 18 -, alternatively C2 to C 10 -, alternatively C2 to C8-, alternatively C2 to C6- olefin units. Non-limiting examples of olefin units include ethylene, propylene, butene, isobutene, pentene, octene-1, and styrene. Generally, polyolefin (a) is polyalkene. Polyolefin (a) can be a homopolymer, such as polyisobutene, or a copolymer of two or more different olefin units. Non-limiting examples of copolymers that can be used to form polyolefin (a) include ethylene and propylene, butene and isobutene, propylene and isobutene. Additional non-limiting examples of copolymers include copolymers containing a small molar amount of olefin units, such as 1 mol% to 10 mol% of C4 to C 18 copolymers of non-conjugated diene units, such as copolymers of isobutene and butadiene or copolymers of ethylene, propylene, and 1,4-hexadiene.

[0269] Polyolefin (a) can be linear or branched. Generally, polyolefin (a) has a number average molecular weight (M n ) of 500 g / mol to 5,000 g / mol, alternatively 750 g / mol to 4,000 g / mol, alternatively 1,000 g / mol to 3,000 g / mol, alternatively 1,000 g / mol to 2,000 g / mol.

[0270] The polyolefin (a) can be saturated or unsaturated. A non-limiting example of a saturated polyolefin (a) is an ethylene-propylene copolymer prepared by Ziegler-Natta synthesis using hydrogen as a moderator to control the molecular weight. However, the polyolefin (a) is generally unsaturated. In a preferred embodiment, the polyolefin (a) contains terminal double bonds.

[0271] To this end, in one embodiment, the polyolefin (a) is reactive polyisobutene. Reactive polyisobutene is generally high-reactivity polyisobutene, which has a high content of terminal olefinic double bonds. The terminal double bonds are α-olefinic double bonds, such as vinylidene double bonds. Reactive polyisobutene generally has a terminal double bond content greater than 50 mol%, alternatively greater than 70 mol%, alternatively greater than 75 mol%, alternatively greater than 80 mol%, alternatively greater than 85 mol%. Reactive polyisobutene generally has a uniform polymer backbone, which contains greater than 85 wt%, alternatively greater than 90 wt%, alternatively greater than 95 wt% of isobutene units.

[0272] Reactive polyisobutene generally has a number-average molecular weight (M n ) of 500 g / mol to 5,000 g / mol, alternatively 800 g / mol to 4,000 g / mol, alternatively 800 g / mol to 3,000 g / mol, alternatively 800 g / mol to 2,000 g / mol. The dispersity D(M w / M n ), that is, the quotient of the weight-average molecular weight M w divided by M n , is less than 7, alternatively less than 3, alternatively 1.05 to 7. In a preferred embodiment, the dispersity D(M w / M n ) of the reactive polyisobutene is less than 3. It is preferred that the reactive polyisobutene has a dispersity less than 2.0 when M n is less than or equal to 2,000 and a dispersity less than 1.5 when M n is less than or equal to 1,000. Reactive polyisobutene generally does not contain organic bases and inorganic bases, water, alcohols, ethers, acids, and peroxides.

[0273] Suitable non-limiting examples of the reactive polyisobutene can be commercially obtained from BASF SE under the brand of polyisobutene.

[0274] C4 to C 10 monounsaturated acid reactant (b)

[0275] C4 to C 10The monounsaturated acid reactant (b) reacts with the polyolefin (a) to form a reaction intermediate (1). The monounsaturated acid reactant (b) is typically an α- or β-unsaturated C4 to C 10 dicarboxylic acid, its anhydride or ester. C4 to C 10 Non-limiting examples of the monounsaturated acid reactant (b) include fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate, chloromaleic anhydride, and combinations thereof.

[0276] In one embodiment, the C4 to C 10 The monounsaturated acid reactant (b) is selected from the group consisting of maleic acid, maleic anhydride, its functional derivatives, and combinations thereof. The term functional derivative describes a derivative of maleic acid or maleic anhydride that reacts with the polyolefin (a) to form the same or a comparable result or product, i.e., the reaction intermediate (1). In the case of maleic acid, the functional derivatives include, for example, monoalkyl maleates, dialkyl maleates, maleoyl dichloride, maleoyl dibromide, monoalkyl maleate monochloride, or monoalkyl maleate monobromide. In the case of maleic esters, the alcohol component is, for example, a lower alkyl having, for example, 1 to 6, especially 1 to 4 carbon atoms, such as methyl or ethyl or n-butyl. In a preferred embodiment, the monounsaturated acid reactant (b) is maleic anhydride. In one embodiment, maleic anhydride reacts with reactive polyisobutylene to form a reaction intermediate (1) comprising polyisobutenyl succinic anhydride.

[0277] Nucleophilic reactant (2)

[0278] As described above, the polyalkenyl succinimide of the present invention comprises the reaction product of a reaction intermediate (1) that produces a hydrocarbyl dicarboxylic acid and a nucleophilic reactant (2). Generally, the polyalkenyl succinimide of the present invention is formed via a neutralization reaction of the nucleophilic reactant (2) with the reaction intermediate (1) that produces a hydrocarbyl dicarboxylic acid. The nucleophilic reactant (2) is generally selected from the group consisting of amines, alcohols, amino alcohols, and combinations thereof.

[0279] The nucleophilic reactant (2) can be a monoamine, oligomeric amine, or polyamine. Since tertiary amines generally do not react with acid anhydrides, it is desirable to have at least one primary or secondary amine group on the amine.

[0280] The nucleophilic reactant (2) can include amines having the following formula Ia or Ib immediately below:

[0281]

[0282] wherein R, R', and R" are independently selected from the group consisting of: hydrogen, C1 to C 25 linear or branched alkyl, C1 to C 12 alkoxy, C2 to C6 alkylene, C2 to C 12 hydroxyamino alkylene, and C2 to C12 Alkylaminoalkylene; each X can be the same or different and is a number from 2 to 6, alternatively from 2 to 4; and Y is a number from 0 to 10, alternatively from 2 to 7, alternatively from 3 to 7.

[0283] In one preferred embodiment, the nucleophilic reactant (2) comprises an amine having the formula II:

[0284] H2N(CH2) x -NH-[(CH2) y -NH] z -(CH2) x NH2 (II)

[0285] wherein x and y are each independently an integer from 1 to 5, alternatively from 2 to 4, and z is an integer from 0 to 8, or a mixture thereof.

[0286] The nucleophilic reactant (2) can include alkylene polyamines such as methylene polyamine, ethylene polyamine, butylene polyamine, propylene polyamine, and pentylene polyamine. In various embodiments, the alkylene polyamine can contain 2 to 40, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 6 total carbon atoms per molecule and 1 to 12, alternatively 2 to 12, alternatively 2 to 9, alternatively 3 to 9 nitrogen atoms. To form the polyalkenyl succinimide of the present invention in such embodiments, typically 0.1 mol to 3.0 mol, alternatively 0.1 mol to 2.0 mol, alternatively 0.2 mol to 1.0 mol, alternatively 0.2 mol to 0.6 mol of succinic acid moiety is reacted per equivalent of the nucleophilic reactant (2) (e.g., amine) to form the polyalkenyl succinimide of the present invention.

[0287] The nucleophilic reactant (2) can also contain polyoxyalkylene polyamines, such as polyoxyalkylene amines, polyoxyalkylene diamines, and polyoxyalkylene triamines having a number average molecular weight (M n ) of 200 g / mol to about 4000 g / mol, alternatively 400 g / mol to 2000 g / mol. Non-limiting examples of polyoxyalkylene polyamines include polyoxyethylene, polyoxypropylene diamines, and polyoxypropylene triamines having a number average molecular weight (M n ) of 200 g / mol to 2000 g / mol.

[0288] In addition, the amino group can be substituted, preferably by an alkyl group, very preferably by a C1-C4 alkyl group. Thus, additional examples include polyoxyalkylene amines having a number average molecular weight (M n) is an N-substituted polyoxyalkyleneamine, N,N,N',N'-tetraalkyl-substituted polyoxyalkylene diamine, and N,N,N',N',N",N"-hexaalkyl-substituted polyoxyalkylene triamine having a weight average molecular weight of from 200 g / mol to about 4000 g / mol, alternatively from 400 g / mol to 2000 g / mol.

[0289] The nucleophilic reactant (2) may also include a hydrocarbylamine or a hydrocarbylamine containing other functional groups such as a hydroxy group, an alkoxy group, an amide group, a nitrile, an imidazolinyl group, etc. For example, in one embodiment, the nucleophilic reactant (2) includes a hydrocarbylamine having from 1 to 6, alternatively from 1 to 3 hydroxy groups. Such amines are capable of reacting with the acid or anhydride groups of the reaction intermediate (1) via their amine functional groups or other functional groups (just described above). Specific non-limiting examples of the nucleophilic reactant (2) include hydroxylamines such as 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, p-(β-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-(β-hydroxypropyl)-N'-(β-amino-ethyl)-piperazine, tris(hydroxymethyl)amino-methane (also known as tris hydroxymethyl amino methane), 2-amino-1-butanol, ethanolamine, β-(β-hydroxyethoxy)-ethylamine, etc.

[0290] The nucleophilic reactant (2) may also include unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexane-3-ol, and oleyl alcohol. Other classes of alcohols capable of producing the inventive polyalkenyl succinimides of the present disclosure include ether alcohols and amino alcohols, such as those substituted with one or more oxyalkylene, aminoalkylene, or aminoaryloxyarylene groups, such as N,N,N',N'-tetrahydroxy-trimethylenediamine, and ether alcohols having up to about 150 oxyalkylene groups, wherein the alkylene contains from 1 to about 8 carbon atoms.

[0291] Additional non-limiting examples of the nucleophilic reactant (2) include alicyclic diamines such as 1,4-bis(aminomethyl)cyclohexane, and heterocyclic nitrogen compounds such as imidazolines and N-aminoalkylpiperazines. Specific non-limiting examples of such amines include 2-pentadecylimidazoline, N-(2-aminoethyl)piperazine, and combinations thereof.

[0292] In one embodiment, the nucleophilic reactant (2) includes a polyamine selected from the group consisting of ethylenediamine, triethylenetetramine, propanediamine, trimethylenediamine, tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, pentaethylenehexamine, and combinations thereof. In this embodiment, the nucleophilic reactant (2) may be the reaction product of dichloroethane and ammonia or the reaction product of ethyleneimine and a ring-opening agent (such as water or ammonia).

[0293] In another embodiment, the nucleophilic reactant (2) includes an ethylene polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. In this embodiment, the ethylene polyamine can be the reaction product of an alkyl chloride with ammonia or ethyleneimine with ammonia. These reactions produce a mixture of alkyl polyamines, including cyclic products such as piperazine.

[0294] Obviously, the various types and combinations of specific embodiments and examples of the nucleophilic reactant (2) mentioned above can react with the reaction intermediate (1) to form the polyalkenyl succinimide of the present invention.

[0295] The polyalkenyl succinimide of the present invention disclosed herein is broadly defined herein to include polyalkenyl succinimide (e.g., polyisobutenyl succinimide), diesters or acid esters of succinic acid (e.g., partially esterified succinic acid), and partially esterified polyols or phenols, such as esters having free alcohol or phenol hydroxyl groups.

[0296] The polyalkenyl succinimide of the present invention can be or include polyisobutenyl succinimide, which includes mono-succinimide and bis-succinimide. The ratio of mono-succinimide to bis-succinimide in polyisobutenyl succinimide can be affected, for example, by changing the molar ratio of the reaction intermediate (1) (e.g., polyisobutenyl succinic anhydride) to the nucleophilic reactant (2) (e.g., amine) that reacts to form the polyalkenyl succinimide (e.g., polyisobutenyl succinimide). The greater the molar amount of the reaction intermediate (1) (e.g., polyisobutenyl succinic anhydride) relative to the nucleophilic reactant (2) (e.g., amine), the greater the amount of the resulting mono-succinimide, and vice versa. To obtain a higher proportion of mono-succinimide, a molar ratio of the reaction intermediate (1) (e.g., polyisobutenyl succinic anhydride) to the nucleophilic reactant (2) (e.g., amine) of 0.7 to 1.3, alternatively 0.9 to 1.1, is typically used. To obtain a higher proportion of bis-succinimide, a molar ratio of the reaction intermediate (1) (e.g., polyisobutenyl succinic anhydride) to the nucleophilic reactant (2) (e.g., amine) of 3 to 18, alternatively 2.3 to 1.9, is typically used. Polyalkenyl succinimide (e.g., polyisobutenyl succinimide) having a higher mono-succinimide content is particularly suitable as an additive for fuels (diesel fuel, heating oil, gasoline fuel), while polyalkenyl succinimide (e.g., polyisobutenyl succinimide) having a higher bis-succinimide content is particularly suitable as an additive for lubricants.

[0297] To form the polyalkenyl succinimide of the present invention, a nucleophilic reactant (2) (e.g., the above-mentioned amine) can be reacted with a reaction intermediate (1) (e.g., alkenyl succinic anhydride) in the following manner: An oil solution containing 5 wt% to 95 wt% of the reaction intermediate (1) is heated to a temperature of 100 to 200 °C, alternatively 125 to 175 °C, for a time of 0.5 to 10 hours, alternatively 1 to 6 hours, to remove any residual water, and the nucleophilic reactant (2) is added. The step of heating the reaction intermediate (1) can promote the formation of an imide or a mixture of imide and amide, rather than the formation of an amide and a salt. The reaction ratio of the reaction intermediate (1) to the amine equivalent and other nucleophilic reactants (2) described herein can vary significantly, depending on the reactants and the type of bonds formed. Generally, for each equivalent of the nucleophilic reactant (2) (e.g., amine), a dicarboxylic acid moiety content (e.g., grafted maleic anhydride content) of 0.1 mol to 2.0 mol, alternatively 0.1 mol to 2.0 mol, alternatively 0.2 mol to 0.6 mol is used. For example, about 0.8 mol of pentamine (having two primary amino groups and 5 equivalents of nitrogen per molecule) can be used to form a mixture of amide and imide, and the product is formed by reacting 1 mol of olefin with maleic anhydride sufficient to add 1.6 mol of succinic anhydride groups / mol of olefin, i.e., preferably, the pentamine is used in an amount sufficient to provide about 0.4 mol (i.e., 1.6 / (0.8×5) mol) of succinic anhydride moiety / equivalent of nitrogen of the amine.

[0298] In a specific embodiment, the polyalkenyl succinimide of the present invention is formed by reacting polyisobutene substituted with succinic anhydride groups with polyvinylamine such as tetraethylenepentamine, pentaethylenehexamine, polyoxyethylene, and polyoxypropyleneamine such as polyoxypropylene diamine, trimethylolethane, trimethylolpropane, and pentaerythritol and combinations thereof. As an example, the polyalkenyl succinimide of the present invention can be formed by reacting polyisobutene substituted with succinic anhydride groups with a hydroxy compound (e.g., pentaerythritol), a polyoxyalkylene polyamine (e.g., polyoxypropylene diamine), and a polyalkylene polyamine (e.g., polyethylene diamine and tetraethylenepentamine).

[0299] In another embodiment, the polyalkenyl succinimide of the present invention comprises the reaction product of polyisobutenyl succinic anhydride, a first amine, and an alcohol. The polyisobutenyl succinic anhydride, the first amine, and the alcohol are generally reacted at a temperature of 50 to 200 °C, alternatively 80 to 180 °C, alternatively 80 to 160 °C, alternatively 100 to 160 °C to form the polyisobutenyl succinimide.

[0300] The first amine generally has the following formula:

[0301] H2N(CH2) x -NH-[(CH2) y -NH]z -(CH2) x NH2

[0302] wherein x and y are each independently an integer from 1 to 5, alternatively from 2 to 4, and z is an integer from 0 to 8, or a mixture thereof.

[0303] The alcohol is selected from the group consisting of monohydric alcohols of the formula R 35 OH, wherein R 35 is a straight-chain, branched-chain, cyclic or branched-cyclic alkyl group having 1 to 16 carbon atoms and combinations thereof. The alcohol is typically a monohydric alcohol, but polyhydric alcohols are also suitable. The alcohol is typically a monohydric alcohol of the formula R 35 OH, wherein R 35 is a straight-chain, branched-chain, cyclic or branched-cyclic alkyl group having 1 to 16, alternatively 6 to 16 carbon atoms.

[0304] Specific non-limiting examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, cyclopropylmethanol, n-butanol, sec-butanol, isobutanol, tert-butanol, 2-hydroxymethylfuran, pentanol, isopentanol, allyl alcohol, cyclohexanol, n-hexanol, 4-methyl-2-pentanol, 2-ethylbutanol, sec-octanol, 2-ethylhexanol, n-decanol, lauryl alcohol, isocetyl alcohol, and mixtures thereof. In one embodiment, the alcohol is 2-ethylhexanol. Additional specific non-limiting examples of the alcohol include phenol, naphthol, (o,p)-alkylphenols (e.g., di-tert-butylphenol), and salicylic acid.

[0305] The molar ratio of polyisobutenyl succinic anhydride to the alcohol can vary. It is not necessary to use a stoichiometric amount of the alcohol, and even a relatively small molar amount of the alcohol can be sufficient to form polyisobutenyl succinimide. Typical molar ratios of polyisobutenyl succinic anhydride to the alcohol are from 10 to 0.5, alternatively from 4 to 0.8.

[0306] In this embodiment, polyisobutenyl succinic anhydride can first react with the alcohol and then with the first amine to form polyisobutenyl succinimide. More specifically, polyisobutenyl succinic anhydride can first react with the alcohol to form a second reaction intermediate comprising a monoester of polyisobutenyl succinic acid, and then the second reaction intermediate reacts with the first amine. In this embodiment, polyisobutenyl succinic anhydride and the alcohol are combined in a reaction vessel. After the reaction of polyisobutenyl succinic anhydride with the alcohol, the first amine can be introduced into the reaction vessel. After the reaction, any unreacted or cleaved alcohol can be removed in a conventional manner.

[0307] In a specific embodiment, the second reaction intermediate comprises the reaction product of: a reactive polyisobutene having a molecular weight M n of 500 g / mol to 5,000 g / mol and a terminal double bond content greater than 50 mol%, alternatively greater than 70 mol%, maleic anhydride, and a compound selected from the group consisting of the formula R35 an alcohol (3) of the group consisting of monohydric alcohols of OH, wherein R 35 is a straight-chain, branched, cyclic or branched-cyclic alkyl group having 1 to 16 carbon atoms.

[0308] If desired, the second reaction intermediate formed during the formation of the polyisobutenyl succinimide can also be separated. This reaction intermediate can be used not only for the formation of the polyalkenyl succinimide of the present invention, but also as an additive for fuels or lubricants alone or in combination with other additives.

[0309] Alternatively, in this embodiment, the separation of the second reaction intermediate is not necessary. That is, the polyisobutenyl succinic anhydride, the first amine and the alcohol react simultaneously, i.e., in a single step, to form the polyisobutenyl succinimide. After the reaction, any unreacted or cleaved alcohol can be removed in a conventional manner.

[0310] In another embodiment, the polyalkenyl succinimide of the present invention can be a reaction product of: a reactive polyisobutene having a molecular weight (M n ) of 500 g / mol to 5,000 g / mol and a terminal double bond content greater than 50 mol%, alternatively greater than 75 mol%, maleic anhydride and a first amine (2) having the following formula:

[0311] H2N(CH2) x -NH-[(CH2) y -NH] z -(CH2) x NH2

[0312] wherein x and y are each independently an integer from 1 to 5, alternatively from 2 to 4, and z is an integer from 0 to 8, or a mixture thereof.

[0313] In another embodiment, the polyalkenyl succinimide of the present invention comprises a reaction product of: a reactive polyisobutene having a number average molecular weight (M n ) of 500 g / mol to 5,000 g / mol and a terminal double bond content greater than 50 mol%, alternatively greater than 70 mol%, maleic anhydride and a straight-chain, branched, cyclic or cyclic-branched alkylene polyamine or a mixture thereof, the straight-chain, branched, cyclic or cyclic-branched alkylene polyamine having 1 to 10, alternatively 2 to 4, carbon atoms in each alkylene group and having 1 to 12, alternatively 2 to 12, alternatively 2 to 9, alternatively 3 to 9 nitrogen atoms, wherein at least one nitrogen atom is present as a primary amino group, and based on the total weight of the product, contains less than 30% by weight of the corresponding polyisobutenyl succinamide.

[0314] In another embodiment, the polyalkenyl succinimide of the present invention comprises the reaction product of a reaction intermediate (1) (e.g., polyisobutenyl succinic anhydride) and a nucleophilic reactant (2), the nucleophilic reactant comprising C2 to C 40 -, optionally C2 to C 20 -, optionally C2 to C 12 - polyalkylene polyamine, the polyalkylene polyamine comprising 2 to 12, optionally 2 to 9, optionally 3 to 9 nitrogen atoms per molecule of amine. To form the polyalkenyl succinimide of the present invention (e.g., polyisobutenyl succinimide) of this embodiment, 0.1 mol to 3.0 mol, optionally 0.2 mol to 1.0 mol, optionally 0.2 mol to 0.6 mol of succinic acid moieties are reacted per equivalent of the nucleophilic reactant (2) (e.g., amine) to form the polyalkenyl succinimide.

[0315] In a typical embodiment, the polyalkenyl succinimide of the present invention has the following structure:

[0316]

[0317] wherein m is an integer from 2 to 80, optionally 2 to 40, optionally 2 to 20, optionally 6 to 16. A typical example of such a polyisobutenyl succinimide is the polyisobutenyl succinimide prepared from polyisobutenyl succinic anhydride and tetraethylenepentamine with M n = 1000 polyisobutenyl.

[0318] The polyalkenyl succinimide of the present invention disclosed herein generally comprises a minimal amount of the corresponding amide (polyisobutenyl succinimide or polyisobutenyl succinic monoamide). More specifically, based on the total weight of the polyalkenyl succinimide of the present invention, the polyalkenyl succinimide of the present invention generally comprises less than 30% by weight, optionally less than 25% by weight, optionally less than 20% by weight, optionally less than 15% by weight of the corresponding amide. In addition, the polyalkenyl succinimide of the present invention generally does not contain an ester fraction, even when the polyalkenyl succinimide comprises the reaction product of a reaction intermediate (1), a nucleophilic reactant (2) and an alcohol (3) as defined above and the reaction with the alcohol (3) is carried out in an intermediate stage. The increased purity (minimal corresponding amide / amide by-products and no ester fraction) of the polyalkenyl succinimide of the present invention is attributed to the method of forming the polyalkenyl succinimide.

[0319] The polyalkenyl succinimide of the present invention generally has a number average molecular weight (M n ) greater than 500 g / mol, alternatively greater than 800 g / mol, alternatively greater than 1,000 g / mol, alternatively from 500 g / mol to 5,000 g / mol, alternatively from 750 g / mol to 5,000 g / mol, alternatively from 1,000 g / mol to 4,000 g / mol, alternatively from 1,000 g / mol to 3,000 g / mol. The hydrophobic moiety of such molecules known in the art can be derived from synthetic or natural mono-fatty acids or oligomeric fatty acids having a chain length generally of C 12 to C 20 . Preferably, the polyalkenyl succinimide of the present invention as described above is formed from a reactive polyisobutene having a chain length generally of C 40 to C 400 , alternatively C 40 to C 200 and a number average molecular weight (M n ) of from 500 g / mol to 5,000 g / mol.

[0320] (A6) Branched amine

[0321] The branched alkylamine R 36 -NH2 is a primary amine bearing an alkyl group R 36 having 8 to 22, preferably 10 to 17, more preferably 13 carbon atoms, and the alkyl group has at least 1.0, preferably 1.0 to 8.0, more preferably 1.5 to 7.0 branches.

[0322] In the context of the present invention, "branch" means that the alkyl residue R 36 contains the required number of branches. In the case of a monoamine having only one branched-chain isomer, the branches of the pure compound can be readily determined based on the chemical structure. In the case of a mixture of isomers, the average branches of the mixture are calculated by adding the branches of each individual isomer multiplied by the molar amount of the corresponding isomer in the mixture. Preferably, the branches are determined using the branching index (ISO index) (see below).

[0323] The branched primary amine can be used as a mixture of amines of different molecular weights or preferably a single molecular weight.

[0324] Typical examples of such amines are the branched isomers of the following amines: octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, and heptadecylamine, preferably nonylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, heptadecylamine, eicosylamine, docosylamine, and mixtures thereof, more preferably nonylamine, tridecylamine, and heptadecylamine, most preferably tridecylamine and heptadecylamine, and especially tridecylamine.

[0325] A preferred example of a branched octylamine is 2-amino-2,4,4-trimethylpentane.

[0326] A preferred example of a branched decylamine is 2-propylheptylamine.

[0327] In a preferred embodiment, the branched amines according to the invention can be obtained by oligomerization of propene, isobutene, 1-butene or 2-butene to form oligomers containing double bonds, followed by hydroformylation and reductive amination with ammonia. The resulting amines are generally mixtures of isomers.

[0328] In another preferred embodiment, the branched amines of the invention can be obtained by amination of the corresponding branched alcohols or by reductive amination of the corresponding branched aldehydes. In this case, the branching of the obtained amines is the same as that of the base alcohols or aldehydes, since the reaction conditions of amination or reductive amination generally do not affect the branching of the alkyl groups.

[0329] In the case of branched tridecylamine, the mixture of isomers can contain one or more of the following isomers:

[0330] 2,2,4,4,6,6-hexamethylheptylamine, 2,4,6-triethylheptylamine, 2,3,4,5,6-pentamethyloctylamine, heptylamine with 2 ethyl groups and 2 methyl groups at the 2, 4, and 6 positions, and heptylamine with 1 ethyl group and 4 methyl groups at the 2, 4, and 6 positions.

[0331] Most preferably, the mixture of isomers is mainly composed of 2,2,4,4,6,6-hexamethylheptylamine or 2,4,6-triethylheptylamine.

[0332] Examples of such mixtures of branched amines are tertiary alkyl C 12 to C 14 amine mixtures (CAS No. 68955-53-3) or C 16 to C 22 amine mixtures.

[0333] Amines having tertiary alkyl groups are less preferred because they exhibit toxicity after inhalation.

[0334] Accordingly, among the branched primary alkylamines according to the invention, preference is given to those amines having an amino group bonded to a primary carbon, i.e. amines bearing the group -CH2-NH2.

[0335] Particular preference is given to the isomeric mixture of tridecylamines obtained from BASF SE (CAS No.: 86089-17-0), which is obtained by amination of the corresponding isomeric mixture of tridecanols having a branching index of 2.2.

[0336] Such branched alkylamines exhibit a lower melting point than the corresponding straight-chain alkylamines and are thus more easily formulated in additive packages. Generally, such branched alkylamines are liquid at room temperature but generally exhibit a lower melting point than the corresponding straight-chain isomers. More easily formulated means that less solvent is required to obtain a homogeneous formulation compared to the corresponding straight-chain alkylamines.

[0337] Accordingly, an object of the present invention is to use such branched primary alkylamines as additives in fuel additive packages in order to improve the storage stability and / or formulatability of gasoline fuel additive packages, the alkyl groups of the branched primary alkylamines having 8 to 22, preferably 10 to 17, more preferably 13 carbon atoms and having at least 1.0, preferably 1.0 to 8.0, more preferably 1.5 to 7.0 branches.

[0338] Branching index (ISO index)

[0339] According to the invention, the degree of branching is preferably described by the ISO index, which represents the average number of branches of the corresponding alkyl group. Thus, for example, in the case of a C8 alkyl group, the n-octyl group contributes 0 to the ISO index, the methylheptyl group contributes 1 to the ISO index, and the dimethylhexyl group contributes 2 to the ISO index. The lower the ISO index, the greater the linearity of the molecules in the corresponding group.

[0340] The degree of branching is defined as the number of methyl groups in the amine molecule minus 1. The average degree of branching is the statistical average of the degrees of branching of the sample molecules. The average degree of branching can preferably be determined by 1 1H-NMR spectroscopy as follows: First, the amine sample is derivatized with trichloroacetyl isocyanate (TAI) (literature: A.K. Bose, P.R. Srinivasan, Tetrahedron 1975, 3025; A. Postma et al., Polymer 2006, 1899). The signal of the methylene group adjacent to the amino group is located at δ = 3 ppm to 4 ppm. All methyl, methylene and methine protons are in the range of 2.4 ppm to 0.4 ppm. Signals < 1 ppm are attributed to methyl groups. The average degree of branching (ISO index) can be calculated from the spectrum obtained in this way as follows:

[0341] ISO index = ((A(CH3) / 3) / (A(CH2-NH2) / 2)) - 1

[0342] Where A(CH3) is the signal area corresponding to the methyl protons and A(CH2-NH2) is the signal area of the methylene protons in the CH2-NH2 group. Primary amines (H2NCHR) with a methine proton adjacent to the amino group can be analyzed similarly. In the case of amines with a quaternary carbon atom adjacent to the amino group, another distinct and assignable proton signal can be used to determine the ISO index.

[0343] In the case of branched amines obtained by amination or reductive amination from the corresponding branched alcohols or aldehydes, the ISO index determined according to the above method can be used.

[0344] Even more preferably 1 The H-NMR method operates without derivatization: The degree of branching (ISO index) of primary amines (H2NCH2R) without α-branching is determined from their 1 H-NMR spectra. All NMR spectra were recorded at T = 298.2 K on a Bruker Avance III 400 spectrometer (operating at 400.33 MHz for 1 H and at 100.66 MHz for 13 C). The spectrometer was equipped with a 5 mm z-gradient broadband observation smart probe. Chemical shifts were referenced to tetramethylsilane (TMS, δ(TMS) = 0 ppm). 1H 1D spectra were recorded using the zg pulse program with 64k data points, the relaxation delay D1 was selected as 5 s, and 64 transients were recorded. For processing in Bruker TopSpin 4.0.9 software, 32k data points were used, and an exponential window function with a line broadening of 0.3 Hz was applied. Automatic baseline correction was used, and phase correction was performed manually by the user. Phase-sensitive HSQC spectra were recorded using the hsqcedetgpsisp2.3 pulse sequence, where there were 4k data points in the direct dimension and 256 data points in the indirect dimension, with 8 transients used for each increment. Optimization experiments were carried out for the 1 J C-H coupling constant of 144 Hz. The relaxation delay D1 was set to 1.0 s. For processing, Fourier transform was performed on 1024×1024 data points, and a quadratic sine function with a sine bell shift of 2 was applied.

[0345] Samples were prepared by dissolving the pure analyte in deuterated chloroform with trace TMS as an internal standard. The samples were transferred to 5 mm NMR tubes. The deuterated solvents were purchased from Euriso-Top GmbH (Euriso-Top) and used as received.

[0346] To determine the ISO index, the integral of H2NCH2R from δ = 2.3 ppm to 2.95 ppm is set to the value 2. The signal of aliphatic methyl groups is integrated from δ = 0.6 ppm to 0.95 ppm (verified by phase-sensitive HSQC spectroscopy) to obtain the value I(Me). The degree of branching (ISO index) is calculated according to ISO index = I(Me) / 3 - 1.

[0347] At least one corrosion inhibitor (B) is selected from the group consisting of:

[0348] -(B1) a hydrolyzed copolymer of an olefin and a carboxylic acid and

[0349] -(B2) a dimer fatty acid.

[0350] Hydrolyzed copolymer of olefin and carboxylic acid (B1)

[0351] The olefin-carboxylic acid copolymer (B1) is a copolymer obtainable by the following steps:

[0352] - copolymerizing the following substances in a first reaction step (I):

[0353] (B1a) at least one ethylenically unsaturated monocarboxylic acid or dicarboxylic acid or a derivative thereof, preferably a dicarboxylic acid,

[0354] (B1b) at least one α-olefin having at least 12 up to and including 30 carbon atoms,

[0355] (B1c) optionally at least one additional aliphatic or cycloaliphatic olefin having at least 4 carbon atoms and different from (B1b), and

[0356] (B1d) optionally one or more additional copolymerizable monomers different from monomers (B1a), (B1b) and (B1c), selected from the group consisting of:

[0357] (B1da) vinyl esters,

[0358] (B1db) vinyl ethers,

[0359] (B1dc) (meth)acrylates of alcohols having at least 5 carbon atoms,

[0360] (B1dd) allyl alcohol or its ethers,

[0361] (B1de) N-vinyl compounds selected from the group consisting of: vinyl compounds containing a heterocycle having at least one nitrogen atom, N-vinylamides or N-vinyl lactams,

[0362] (B1df) ethylenically unsaturated aromatic compounds,

[0363] (B1dg) α,β-ethylenically unsaturated nitrile,

[0364] (B1dh) (meth)acrylamide and

[0365] (B1di) allylamine,

[0366] Subsequently

[0367] - In a second optional reaction step (II), partially or completely hydrolyzing and / or saponifying the anhydride or carboxylic acid ester functional groups present in the copolymer obtained from (I), this second reaction step being carried out at least when the copolymer obtained from reaction step (I) does not contain any free carboxylic acid functional groups.

[0368] Description of copolymer (B1)

[0369] Monomer (B1a) is at least one, preferably one to three, more preferably one or two and most preferably exactly one ethylenically unsaturated, preferably α,β-ethylenically unsaturated monocarboxylic or dicarboxylic acid or a derivative thereof, preferably a dicarboxylic acid or a derivative thereof.

[0370] The derivative is to be understood to mean:

[0371] - The corresponding anhydride in monomer or polymer form,

[0372] - Mono- or dialkyl esters, preferably mono- or di C1-C4 alkyl esters, more preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, and

[0373] - Mixed esters, preferably mixed esters having different C1-C4 alkyl components, more preferably mixed methyl ethyl esters.

[0374] Preferably, the derivative is an anhydride or a di C1-C4 alkyl ester in monomer form, more preferably an anhydride in monomer form.

[0375] In the context of this document, C1-C4 alkyl is to be understood to mean methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl and ethyl, more preferably methyl.

[0376] Examples of α,β-ethylenically unsaturated monocarboxylic or dicarboxylic acids are those monocarboxylic or dicarboxylic acids or derivatives thereof in which the carboxyl group or, in the case of a dicarboxylic acid, at least one carboxyl group, preferably two carboxyl groups, is conjugated with an ethylenically unsaturated double bond.

[0377] Examples of ethylenically unsaturated monocarboxylic or dicarboxylic acids that are not α,β-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-dicarboxylic anhydride.

[0378] Examples of α,β-ethylenically unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, crotonic acid, and ethacrylic acid, preferably acrylic acid and methacrylic acid (abbreviated as (meth)acrylic acid in this document), and more preferably acrylic acid.

[0379] Particularly preferred derivatives of α,β-ethylenically unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate.

[0380] Examples of dicarboxylic acids are maleic acid, fumaric acid, itaconic acid (2-methylenesuccinic acid), citraconic acid (2-methylmaleic acid), glutaconic acid (pent-2-ene-1,5-dicarboxylic acid), 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3-dimethylfumaric acid, methylenemalonic acid, and tetrahydrophthalic acid, preferably maleic acid and fumaric acid, and more preferably maleic acid and its derivatives.

[0381] More specifically, monomer (B1a) is maleic anhydride.

[0382] Monomer (B1b) is at least one, preferably one to four, more preferably one to three, even more preferably one or two, and most preferably exactly one α-olefin having at least 12 up to and including 30 carbon atoms. The α-olefin (B1b) preferably has at least 14, more preferably at least 16, and most preferably at least 18 carbon atoms. Preferably, the α-olefin (B1b) has at most and including 28, more preferably at most and including 26, and most preferably at most and including 24 carbon atoms.

[0383] Preferably, the α-olefin can be one or more straight-chain or branched-chain, preferably straight-chain 1-olefins.

[0384] Examples of these are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene, preferably 1-octadecene, 1-eicosene, 1-docosene, and 1-tetracosene and mixtures thereof.

[0385] Further examples of α-olefins (B1b) are those olefins that are oligomers or polymers of C2 to C 12 olefins, preferably C3 to C 10 olefins, more preferably C4 to C6 olefins. Examples thereof are ethylene, propylene, 1-butene, 2-butene, isobutene, pentene isomers, and hexene isomers, preferably ethylene, propylene, 1-butene, 2-butene, and isobutene.

[0386] Examples of the naming of α-olefins (B1b) include oligomers and polymers of propylene, 1-butene, 2-butene, isobutene, and mixtures thereof, especially oligomers and polymers of propylene or isobutene or mixtures of 1-butene and 2-butene. Among these oligomers, trimers, tetramers, pentamers, hexamers, and mixtures thereof are preferred.

[0387] In addition to the olefin (B1b), optionally, at least one, preferably one to four, more preferably one to three, even more preferably one or two, and especially exactly one additional aliphatic or cycloaliphatic olefin (B1c) having at least 4 carbon atoms and different from (B1b) can be incorporated into the copolymer of the present invention by polymerization.

[0388] The olefin (B1c) can be an olefin having a terminal (α-) double bond or an olefin having a non-terminal double bond, preferably an olefin having an α-double bond. The olefin (B1c) preferably includes olefins having 4 to less than 12 or more than 30 carbon atoms. If the olefin (B1c) is an olefin having 12 to 30 carbon atoms, then the olefin (B1c) does not have an α-double bond.

[0389] Examples of aliphatic olefins (B1c) are 1-butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers, and mixtures thereof.

[0390] Examples of cycloaliphatic olefins (B1c) are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, α- or β-pinene and mixtures thereof, limonene, and norbornene.

[0391] Another example of the olefin (B1c) is a polymer of propylene, 1-butene, 2-butene, or isobutene having more than 30 carbon atoms or an olefin mixture containing the latter, preferably a polymer of isobutene or an olefin mixture containing the latter, more preferably having an average molecular weight M of 500 g / mol to 5000 g / mol, preferably 650 g / mol to 3000 g / mol, and more preferably 800 g / mol to 1500 g / mol w 。

[0392] Preferably, the oligomers or polymers containing isobutene in copolymerized form have a high content of terminal olefinic double bonds (α-double bonds), such as at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, and most preferably at least 80 mol%.

[0393] To prepare such oligomers or polymers containing isobutene in copolymerized form, suitable sources of isobutene are pure isobutene or C4 hydrocarbon streams containing isobutene, such as C4 raffinates, especially "raffinate 1", C4 fractions from isobutane dehydrogenation, C4 fractions from steam crackers and from FCC crackers (fluid catalytic cracking), provided that they are substantially free of 1,3-butadiene present therein. The C4 hydrocarbon stream from the FCC refining unit is also referred to as the "b / b" stream. Also suitable C4 hydrocarbon streams containing isobutene are, for example, product streams from the co-oxidation of propylene-isobutane or product streams from metathesis units, which are usually used after conventional purification and / or concentration. Suitable C4 hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm, of butadiene. The presence of 1-butene and cis- and trans-2-butene is substantially immaterial. Generally, the isobutene concentration in the C4 hydrocarbon stream is in the range of 40 wt% to 60 wt%. For example, raffinate 1 generally consists essentially of 30 wt% to 50 wt% isobutene, 10 wt% to 50 wt% 1-butene, 10 wt% to 40 wt% cis- and trans-2-butene, and 2 wt% to 35 wt% butane; during the polymerization, the unbranched butenes in raffinate 1 are generally almost inert and only the isobutene is polymerized.

[0394] In a preferred embodiment, the monomer source for the polymerization is an industrial C4 hydrocarbon stream having an isobutene content of 1 wt% to 100 wt%, especially 1 wt% to 99 wt%, particularly 1 wt% to 90 wt%, more preferably 30 wt% to 60 wt%, especially the raffinate 1 stream, the b / b stream from the FCC refining unit, the product stream from the co-oxidation of propylene-isobutane or the product stream from the metathesis unit.

[0395] Especially when the raffinate 1 stream is used as the isobutene source, it has been found useful to use water as the sole initiator or as an additional initiator, especially when the polymerization is carried out at a temperature of -20 °C to +30 °C, especially 0 °C to +20 °C. However, at a temperature of -20 °C to +30 °C, especially 0 °C to +20 °C, when using the raffinate 1 stream as the isobutene source, the use of an initiator can be dispensed with.

[0396] The isobutene-containing monomer mixture may contain small amounts of contaminants such as water, carboxylic acids or mineral acids without any significant loss of yield or selectivity. It is appropriate to avoid the accumulation of these impurities by removing these harmful substances from the isobutene-containing monomer mixture (e.g., by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers).

[0397] Although less preferred, it is also possible to convert a monomer mixture of isobutene or an isobutene-containing hydrocarbon mixture and an ethylenically unsaturated monomer copolymerizable with isobutene. If the monomer mixture of isobutene and a suitable comonomer is to be copolymerized, the monomer mixture preferably contains 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 the comonomer.

[0398] In a preferred embodiment, the mixture of olefins (B1b) and optionally (B1c) (taking the average according to their molar amounts) has at least 12 carbon atoms, preferably at least 14, more preferably at least 16 and most preferably at least 17 carbon atoms.

[0399] For example, a 2:3 mixture of docosene and tetradecene has an average number of carbon atoms of 0.4×22 + 0.6×14 = 17.2.

[0400] The upper limit is less relevant and generally does not exceed 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.

[0401] The optional monomer (B1d) is at least one monomer, preferably one to three, more preferably one or two and most preferably exactly one monomer selected from the group consisting of:

[0402] (B1da) vinyl esters,

[0403] (B1db) vinyl ethers,

[0404] (B1dc) (meth)acrylates of alcohols having at least 5 carbon atoms,

[0405] (B1dd) allyl alcohol or its ethers,

[0406] (B1de) N-vinyl compounds selected from the group consisting of: vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-vinyl lactams,

[0407] (B1df) ethylenically unsaturated aromatic compounds and

[0408] (B1dg) α,β-ethylenically unsaturated nitriles,

[0409] (B1dh) (meth)acrylamides and

[0410] (B1di) allylamine.

[0411] Examples of vinyl esters (B1da) are C2 to C 12Vinyl esters of carboxylic acids, preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl caproate, vinyl caprylate, vinyl 2-ethylhexanoate, vinyl decanoate, and vinyl esters of tertiary carbonic acids having 5 to 10 carbon atoms, preferably vinyl 2,2-dimethylpropionate (pivalic acid, tertiary carbonic acid 5), vinyl 2,2-dimethylbutyrate (neohexanoic acid, tertiary carbonic acid 6), vinyl 2,2-dimethylvalerate (neoheptanoic acid, tertiary carbonic acid 7), vinyl 2,2-dimethylcaproate (neooctanoic acid, tertiary carbonic acid 8), vinyl 2,2-dimethylheptanoate (neononanoic acid, tertiary carbonic acid 9), or vinyl 2,2-dimethyloctanoate (neodecanoic acid, tertiary carbonic acid 10).

[0412] Examples of vinyl ethers (B1db) are vinyl ethers of C1 to C 12 alkanols, preferably vinyl ethers of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), or 2-ethylhexanol.

[0413] Preferred (meth)acrylates (B1dc) are (meth)acrylates of C5 to C 12 alkanols, preferably (meth)acrylates of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, or 2-propylheptanol. Particularly preferred are pentyl acrylate, 2-ethylhexyl acrylate, and 2-propylheptyl acrylate.

[0414] Examples of monomers (B1dd) are allyl alcohols and allyl ethers of C2 to C 12 alkanols, preferably allyl ethers of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), or 2-ethylhexanol.

[0415] Examples of vinyl compounds (B1de) of heterocycles containing at least one nitrogen atom are N-vinylpyridine, N-vinylimidazole, and N-vinylmorpholine.

[0416] Preferred compounds (B1de) are N-vinylamides or N-vinyl lactams.

[0417] Examples of N-vinylamides or N-vinyl lactams (B1de) are N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, and N-vinylcaprolactam.

[0418] Examples of ethylenically unsaturated aromatic compounds (B1df) are styrene and α-methylstyrene.

[0419] Examples of α,β-ethylenically unsaturated nitriles (B1dg) are acrylonitrile and methacrylonitrile.

[0420] Examples of (meth)acrylamide (B1dh) are acrylamide and methacrylamide.

[0421] Examples of allylamine (B1di) are allylamine, dialkylallylamine, and trialkylallylammonium halide.

[0422] Preferred monomers (B1d) are (B1da), (B1db), (B1dc), (B1de), and / or (B1df), more preferably (B1da), (B1db), and / or (B1dc), even more preferably (B1da) and / or (B1dc), and especially (B1dc).

[0423] The incorporation ratios of monomers (B1a) and (B1b) and optionally (B1c) and optionally (B1d) in the polymer obtained from reaction step (I) are generally as follows:

[0424] The molar ratio of (B1a) / ((B1b) and (B1c)) (total) is generally from 10:1 to 1:10, preferably from 8:1 to 1:8, more preferably from 5:1 to 1:5, even more preferably from 3:1 to 1:3, especially from 2:1 to 1:2, and particularly from 1.5:1 to 1:1.5. In a preferred specific case where maleic anhydride is monomer (B1a), the molar incorporation ratio of maleic anhydride to monomer ((B1b) and (B1c)) (total) is about 1:1.

[0425] The molar ratio of the essential monomer (B1b) to monomer (B1c) (if present) is generally from 1:0.05 to 10, preferably from 1:0.1 to 6, more preferably from 1:0.2 to 4, even more preferably from 1:0.3 to 2.5, and especially from 1:0.5 to 1.5.

[0426] In a preferred embodiment, there is no optional monomer (B1c) in addition to monomer (B1b).

[0427] Based on the amount of monomers (B1a), (B1b), and optionally (B1c) (total), the proportion of one or more monomers (B1d) (if present) is generally from 5 mol% to 200 mol%, preferably from 10 mol% to 150 mol%, more preferably from 15 mol% to 100 mol%, even more preferably from 20 mol% to 50 mol%, and especially from 0 mol% to 25 mol%.

[0428] In a preferred embodiment, there is no optional monomer (B1d).

[0429] In the second reaction step (II), the anhydride or carboxylic acid ester functional groups present in the copolymer obtained from (I) are partially or completely hydrolyzed and / or saponified.

[0430] In the case where the copolymer obtained in reaction step (I) does not contain free carboxylic acid groups, reaction step (II) is necessary.

[0431] The hydrolysis of acid anhydride groups is preferred over the saponification of ester groups.

[0432] Preferably, 10% to 100% of the acid anhydride or carboxylic acid ester functional groups present are hydrolyzed and / or saponified, preferably at least 20%, more preferably at least 30%, even more preferably at least 50%, especially at least 75%, and in particular at least 85%.

[0433] For hydrolysis, an amount of water corresponding to the desired level of hydrolysis is added based on the acid anhydride functional groups present, and the copolymer obtained in (I) is heated in the presence of the added water. Generally speaking, a temperature of 20 to 150 °C is preferably sufficient for this purpose, preferably 60 to 100 °C. If necessary, the reaction can be carried out under pressure to prevent the escape of water. Under these reaction conditions, generally speaking, the acid anhydride functional groups in the copolymer are selectively converted, while any carboxylic acid ester functional groups present in the copolymer react at least only to a minor extent (if at all).

[0434] For saponification, the copolymer is reacted with an amount of strong base corresponding to the desired level of saponification in the presence of water.

[0435] The strong base used can preferably be a hydroxide, oxide, carbonate or bicarbonate of an alkali metal or alkaline earth metal.

[0436] The copolymer obtained in (I) is then heated in the presence of the added water and the strong base. Generally speaking, a temperature of 20 to 130 °C is preferably sufficient for this purpose, preferably 50 to 110 °C. If necessary, the reaction can be carried out under pressure.

[0437] The carboxylic acid ester functional groups can also be hydrolyzed with water in the presence of an acid. The acid used is preferably a mineral acid, carboxylic acid, sulfonic acid or phosphoric acid with a pKa not exceeding 5, more preferably not exceeding 4.

[0438] Examples are acetic acid, formic acid, oxalic acid, salicylic acid, substituted succinic acid, aromatic substituted or unsubstituted benzenesulfonic acid, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; the use of acidic ion exchange resins is also conceivable.

[0439] In a preferred embodiment where the acid anhydride, especially maleic anhydride, is monomer (B1a), such acid anhydride moieties are partially or completely, especially completely, hydrolyzed, while the ester groups potentially present in the copolymer remain intact. In this case, no saponification occurs in step (II).

[0440] The copolymer obtained from (I) is then heated in the presence of added water and acid. Generally speaking, a temperature of from 40 °C to 200 °C is preferably sufficient for this purpose, more preferably from 80 °C to 150 °C. If desired, the reaction can be carried out under pressure.

[0441] If the copolymer obtained from step (II) still contains residues of acid anions, these acid anions can preferably be removed from the copolymer by means of an ion exchanger and preferably exchanged for hydroxide ions or carboxylate ions, more preferably hydroxide ions. This is especially the case when the acid anions present in the copolymer are halide ions or contain sulfur or nitrogen.

[0442] The copolymer obtained from reaction step (II) generally has a weight-average molecular weight Mw of from 0.5 kDa to 20 kDa, preferably from 0.6 kDa to 15 kDa, more preferably from 0.7 kDa to 7 kDa, even more preferably from 1 kDa to 7 kDa and especially from 1.5 kDa to 4 kDa (determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standards).

[0443] The number-average molecular weight Mn is generally from 0.5 kDa to 10 kDa, preferably from 0.6 kDa to 5 kDa, more preferably from 0.7 kDa to 4 kDa, even more preferably from 0.8 kDa to 3 kDa and especially from 1 kDa to 2 kDa (determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standards).

[0444] 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.

[0445] The acid group content in the copolymer is preferably from 1 mmol / g copolymer to 8 mmol / g copolymer, more preferably from 2 mmol / g copolymer to 7.5 mmol / g copolymer, even more preferably from 3 mmol / g copolymer to 7 mmol / g copolymer.

[0446] In a preferred embodiment, the copolymer contains a high proportion of adjacent carboxylic acid groups, which is determined by measuring the degree of adjacency. For this purpose, a copolymer sample is heat-treated for a period of 30 minutes at a temperature of 290 °C between two Teflon films, and an FTIR spectrum is recorded at bubble-free sites. The IR spectrum of Teflon is subtracted from the spectrum obtained, the layer thickness is determined and the content of cyclic anhydrides is determined.

[0447] In a preferred embodiment, the degree of 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%.

[0448] The olefin-carboxylic acid copolymer (B1) is applied in the form of the free acid (i.e., the COOH group is present), or in the form of the acid anhydride (the acid anhydride can be an intramolecular acid anhydride or an intermolecular acid anhydride that links two dicarboxylic acid molecules), preferably in the form of the free acid. To a lesser extent, some of the carboxylic acid functional groups can be present in the form of salts, such as as a base or an alkali metal salt or as an ammonium salt or a substituted ammonium salt, depending on the pH value of the liquid phase. Preferably, at least 50%, more preferably at least 66%, very preferably at least 75%, even more preferably at least 85% and especially at least 95% of all the carboxylic acid groups are present in the form of the free acid as the COOH-group. A single olefin-carboxylic acid copolymer (B1) or a mixture of different olefin-carboxylic acid copolymers (B1) can be used.

[0449] (B2) Dimer fatty acid

[0450] Dimer fatty acids are dimers of unsaturated monocarboxylic acids having 9 to 30 carbon atoms, preferably 12 to 28, more preferably 14 to 26, even more preferably 16 to 24 and especially 18 to 20 carbon atoms. The unsaturated monocarboxylic acid can carry one, two or more double bonds, preferably one or two, even more preferably one double bond, especially selected from the group consisting of myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, isolenic acid, linoleic acid, trans-linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid, preferably selected from the group consisting of palmitoleic acid, oleic acid, linoleic acid and α-linolenic acid, more preferably selected from the group consisting of palmitoleic acid, oleic acid and linoleic acid.

[0451] Such dimers generally contain 20 to 60 carbon atoms, preferably 24 to 44, more preferably 28 to 40 and especially 32 to 38 carbon atoms.

[0452] The dimer can contain a small amount of trimers or higher oligomers of the unsaturated monocarboxylic acid.

[0453] Dimerization and oligomerization are generally carried out by the Diels-Alder reaction, such that the dimer generally contains at least one substituted cyclohexene substructure. Oligomerization can also be carried out by the Alder ene reaction or free radical oligomerization.

[0454] (B3) Amide of aliphatic or aromatic carboxylic acid

[0455] The amide (B3) is a reaction product of an aliphatic or aromatic carboxylic acid (B3a) and a primary or secondary amine (B3b) having at least one additional functional group selected from the group consisting of a carboxylic acid group, a sulfonic acid group and an amino group.

[0456] The aliphatic carboxylic acid (B3a) is preferably an aliphatic monocarboxylic acid, more preferably a fatty acid containing 12 to 30 carbon atoms, even more preferably selected from the group consisting of dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid, trans-linoleic acid, erucic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid, preferably tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid, trans-linoleic acid, erucic acid, arachidic acid and behenic acid, very preferably hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid and trans-linoleic acid, and especially preferably oleic acid, linoleic acid and trans-linoleic acid. Oleic acid is particularly preferred.

[0457] The aromatic carboxylic acid (B3a) contains 7 to 30 carbon atoms and may carry 1 or 2, preferably 1, carboxylic acid group. Preferred examples are benzoic acid, 1- or 2-naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, each of which is optionally substituted by a C1 to C 20 alkyl group. Very preferably, the aromatic carboxylic acid (B3a) is selected from the group consisting of benzoic acid, 1- and 2-naphthoic acid.

[0458] The amine (B3b) is a primary or secondary amine carrying at least one additional functional group selected from the group consisting of a carboxylic acid group, a sulfonic acid group and an amino group.

[0459] Examples of such amines carrying at least one additional amino group are 1,3-propanediamine, 3-(N,N-dimethylamino)propanediamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, more preferably ammonia, dimethylamine, diethylenetriamine or triethylenetetramine.

[0460] Examples of such amines carrying at least one additional sulfonic acid group are taurine, m-aminobenzenesulfonic acid, 3-aminoethylsulfonic acid and 3-aminopropylsulfonic acid.

[0461] Examples of such amines carrying at least one additional carboxylic acid group are amino acids, especially glycine, alanine, 3-aminopropionic acid, N-methylglycine, salicylic acid and 4-aminobenzoic acid.

[0462] Preferred examples of (B3) are oleoyl sarcosine (CAS No. 110-25-8) and the reaction product of naphthenic acid and diethylenetriamine (CAS No. 68131-13-5).

[0463] Carrier oil (C)

[0464] The carrier oil can be of mineral or synthetic nature. Suitable mineral carrier oils are fractions obtained in the processing of crude oil, such as bright oils or base oils having a viscosity of, for example, SN 500 - 2000 grade; and aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Also useful are fractions obtained in the refining of mineral oils and called "hydrocracked oils" (vacuum distillates with a boiling range of about 360 to 500 °C, which can be obtained from natural mineral oils that have been catalytically hydrogenated, isomerized and dewaxed under high pressure). Also suitable are mixtures of the above mineral carrier oils.

[0465] Examples of suitable synthetic carrier oils are polyolefins (poly-α-olefins or polyinternal olefins), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, polyethers starting from alkylphenols, polyetheramines starting from alkylphenols and carboxylic esters of long-chain alkanols.

[0466] Examples of suitable polyolefins are M n olefin polymers with M = 400 to 1800, especially olefin polymers based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

[0467] Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C2 to C4 alkylene moieties, which can be obtained by reacting C2 to C 60 alkanols, C6 to C 30 alkanediols, mono- or di-C2 to C 30 alkylamines, C1 to C 30 alkylcyclohexanols or C1 to C 30 alkylphenols with 1 mol to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group, and in the case of polyetheramines, subsequently reductive amination with ammonia, monoamines or polyamines. Such products are described in more detail in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A4,877,416. For example, the polyetheramines used can be poly-C2 to C6 alkyleneamines or their functional derivatives. Typical examples thereof are tridecanol butoxylates or isotridecanol butoxylates, heptadecanol butoxylates or isoheptadecanol butoxylates, tridecanol propoxylates or isotridecanol propoxylates, heptadecanol propoxylates or isoheptadecanol propoxylates, isononylphenol butoxylates, and polyisobutenol butoxylates and propoxylates, and the corresponding reaction products with ammonia.

[0468] Examples of carboxylic acid esters of long-chain alkanols are more particularly esters of monocarboxylic acids, dicarboxylic acids or tricarboxylic acids with long-chain alkanols or polyols, as described in more detail in DE-A 38 38 918. The monocarboxylic acids, dicarboxylic acids or tricarboxylic acids used can be aliphatic acids or aromatic acids; particularly suitable ester alcohols or ester polyols are the long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipic acid esters, phthalic acid esters, isophthalic acid esters, terephthalic acid esters and trimellitic acid esters of isooctanol, isononanol, isodecanol and isotridecanol, such as bis(n- or isotridecyl) phthalate.

[0469] Further suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 4309 074, EP-A 452 328 and EP-A 548 617.

[0470] Particularly suitable synthetic carrier oils are alcohol-initiated polyethers, each alcohol molecule having about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and especially 15 to 30 C3 to C6 alkylene oxide units, such as propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof. Non-limiting examples of suitable starting alcohols are long-chain alkanols or phenols substituted by long-chain alkyl groups, where the long-chain alkyl groups are especially straight-chain or branched C6 to C 18 alkyl groups. Specific examples include tridecanol, heptadecanol and nonylphenol. Particularly preferred alcohol-initiated polyethers are the reaction products (polyetherification products) of monohydric aliphatic C6 to C 18 alcohols with C3 to C6 alkylene oxides. Examples of monohydric aliphatic C6-C 18 alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol and their structural and positional isomers. The alcohols can be used in the form of pure isomers or in the form of industrial-grade mixtures. Particularly preferred alcohols are tridecanol. Examples of C3 to C6 alkylene oxides are propylene oxide (such as 1,2-propylene oxide), butylene oxide (such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran), pentylene oxide and hexylene oxide. Particularly preferred among them are C3 to C4 alkylene oxides, namely propylene oxide (such as 1,2-propylene oxide) and butylene oxide (such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide). In particular, butylene oxide and mixtures of butylene oxide and propylene oxide are used.

[0471] Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.

[0472] Specific carrier oils are synthetic carrier oils, and particularly preferred are the above-mentioned alcohol-initiated polyethers.

[0473] In a preferred embodiment, the carrier oil is a C straight-chain or branched-chain alcohol alkoxylated 5 to 30 times 10 to C 20 alkanol, preferably a straight-chain or branched-chain C 12 to C 18 alkanol, more preferably a branched-chain C 13 to C 17 alkanol, and is alkoxylated with ethylene oxide, propylene oxide, and / or butylene oxide, preferably propylene oxide and / or butylene oxide.

[0474] In another preferred embodiment, the carrier oil is a polyetheramine obtainable by the following steps: aminating the above alkoxylated alkanol (i.e., a C straight-chain or branched-chain alcohol alkoxylated 5 to 30 times 10 to C 20 alkanol, preferably a straight-chain or branched-chain C 12 to C 18 alkanol, more preferably a branched-chain C 13 to C 17 alkanol), and alkoxylating with ethylene oxide, propylene oxide, and / or butylene oxide, preferably propylene oxide and / or butylene oxide, and subsequently aminating the alkoxylated alkanol thus obtained.

[0475] Such polyetheramines are described, for example, in US 5660601.

[0476] Cloud point depressant (D)

[0477] Suitable cloud point depressants are, for example, alkali metal salts or alkaline earth metal salts of alkyl-substituted phenolsulfonic acids and naphthalenesulfonic acids and alkali metal salts or alkaline earth metal salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates (e.g., alcohol ethoxylates), phenol alkoxylates (e.g., tert-butylphenol ethoxylate or tert-amylphenol ethoxylate), fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO) (e.g., in the form of EO / PO block copolymers), polyethyleneimine, alkoxylated polyethyleneimine, or polysiloxanes.

[0478] Also suitable cloud point depressants are EO / PO-based alkoxylates of alkylphenol-formaldehyde condensates (novolacs, resoles, or calixarene types), diols (e.g., propylene glycol, ethylene glycol), triols (e.g., glycerol or trimethylolpropane), EO / PO-based alkoxylates of ethylenediamine or polyethyleneimine. Also suitable cloud point depressants are alkylbenzenesulfonic acids, dialkyl sulfosuccinates, or their alkali metal salts or ammonium salts. Suitable cloud point depressants are described in WO 96 / 22343. Also suitable diglycidyl ether-based cloud point depressants are described in US 3383326 and US 3511882.

[0479] Other suitable de-turbidizing agents are, for example, alkoxylated phenol-formaldehyde condensates, such as products available under the trade names NALCO 7D07 (Nalco Company) and TOLAD 2683 (Petrolite Corporation).

[0480] In a preferred embodiment, the de-turbidizing agent (D) is selected from the group consisting of:

[0481] -- (D1) alkoxylated polyethyleneimine,

[0482] -- (D2) alkylphenolic resin and

[0483] -- (D3) alkyl-, aryl- or alkylaryl sulfonates or sulfates.

[0484] Alkoxylated polyethyleneimine (D1)

[0485] Component (D1) is at least one alkoxylated polyethyleneimine of the following formula polyethyleneimine: Formula (IV)

[0486]

[0487] or Formula (V)

[0488]

[0489] And

[0490] Where

[0491] For X where i = 1 to j, 1 to k, 1 to l, 1 to m, 1 to n, 1 to p, 1 to q, 1 to r or 1 to s iIndependently 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-, and most preferably selected from the group consisting of -CH2-CH2-O-, -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-, and in particular selected from the group consisting of -CH2-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-

[0492] x and y are independently zero or a positive integer

[0493] j, k, l, m, n, p, q and r are independently zero or a positive integer

[0494] wherein

[0495] provided that

[0496] - the sum of x and y in formula (V) is non-zero

[0497] - the sum of j, k, l, m, n, p, q and r is non-zero.

[0498] The precursors of alkoxylated monomeric ethylenimines, low-polyethylenimines and polyethylenimines to be used in the context of the present invention are branched amines, monomeric amines, oligomeric amines or polymeric amines, wherein the nitrogen atom is always followed by two carbon atoms.

[0499] In formula (IV) representing alkoxylated monomeric ethylenimines and low-polyethylenimines, typical values of x are zero or from 1 to 5, more preferably zero or from 1 to 4, even more preferably zero or from 1 to 3, and in particular zero or 1 or 2.

[0500] Examples of monomeric ethylenimine and low-polyethylenimine are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. When there are more than five ethylenimine units, these compounds are called polyethylenimine.

[0501] In formula (V) representing alkoxylated polyethylenimine, typical values of x and y are, independently of each other, zero or from 1 to 1500, more preferably from 10 to 1400, even more preferably from 20 to 1300, and especially from 30 to 1200.

[0502] Provided that the sum of x and y in formula (V) is non-zero.

[0503] By 13 Determined by 13C-NMR spectroscopy, in the polyethylenimine which is the basis of the alkoxylated polyethylenimine, the ratio of primary nitrogen atoms to secondary nitrogen atoms to tertiary nitrogen atoms is preferably from 1:0.5 to 1.5:0.3 to 0.9, preferably from 1:0.6 to 1.3:0.4 to 0.8, more preferably from 1:0.7 to 1.3:0.4 to 0.8, and especially from 1:0.9 to 1.1:0.5 to 0.7, as typical in the corresponding commercially available products. As polymers, they have a molecular weight distribution. In the context of the present invention, it is preferred to use those types of polyethylenimine having an average molar mass (Mw measured by GPC) of less than 55 000 g / mol, preferably less than 50 000 g / mol, more preferably less than 40 000 g / mol, even more preferably less than 30 000 g / mol. The idealized formulas (IV) and (V) illustrate the structure of commercial branched polyethylenimine, in which the average ratio of primary nitrogen atoms to secondary nitrogen atoms to tertiary nitrogen atoms is about 1:2:1. Preferred polyethylenimines have the above-mentioned preferred ratio of primary nitrogen atoms to secondary nitrogen atoms to tertiary nitrogen atoms.

[0504] Monomeric ethylenimine, low-polyethylenimine or polyethylenimine is alkoxylated with a C2 to C4 alkylene oxide or a mixture of these alkylene oxides such that the alkoxylated monomeric ethylenimine, low-polyethylenimine or polyethylenimine has a preferred degree of alkoxylation, i.e. the sum of j, k, l, m, n, p, q and r is from 2 to 200 alkylene oxide units, preferably from 5 to 180, more preferably from 10 to 150, most preferably from 15 to 100, and especially from 20 to 50.

[0505] The degree of alkoxylation of each free NH group, i.e. the parameters j, k, l, m, n, p, q and r are, independently of each other, zero or a positive integer, provided that the sum of j, k, l, m, n, p, q and r is non-zero. The preferred values of the parameters j, k, l, m, n, p, q and r are, independently of each other, zero or from 1 to 50, more preferably zero or from 1 to 40, even more preferably from 1 to 35, and especially from 2 to 30.

[0506] Specifically, the alkoxylated monomeric ethyleneimine, low-polyethyleneimine or polyethyleneimine used is prepared by successively alkoxylating ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide and / or isobutylene oxide, preferably ethylene oxide, propylene oxide and / or 1-butylene oxide, more preferably ethylene oxide and / or propylene oxide, under base catalysis.

[0507] Preferred are those alkoxylated monomeric ethyleneimines, low-polyethyleneimines or polyethyleneimines which are prepared by first alkoxylating with propylene oxide (PO) and subsequently with ethylene oxide (EO).

[0508] The alkoxylation with two or more different alkylene oxides (preferably with two different alkylene oxides) can be carried out in a statistical or block manner, preferably in a statistical manner.

[0509] Measured by gel permeation chromatography (GPC) relative to polyethylene glycol in tetrahydrofuran, compound (D1) generally has a weight-average molecular weight Mw of from 2,000 g / mol to 5,000,000 g / mol, preferably from 3,000 g / mol to 4,500,000 g / mol, more preferably from 4,000 g / mol to 3,000,000 g / mol, even more preferably from 5,000 g / mol to 2,500,000 g / mol and most preferably from 6,000 g / mol to less than 2,000,000 g / mol.

[0510] In one embodiment of the present invention, compound (D1) exhibits a weight-average molecular weight M determined by gel permeation chromatography of less than 55,000 g / mol, preferably less than 50,000 g / mol, more preferably less than 45,000 g / mol, even more preferably less than 40,000 g / mol, most preferably less than 35,000 g / mol and especially less than 30,000 g / mol w .

[0511] In another embodiment of the present invention, compound (D1) exhibits a weight-average molecular weight M determined by gel permeation chromatography of greater than 55,000 g / mol, preferably greater than 100,000 g / mol, more preferably greater than 200,000 g / mol and especially greater than 500,000 g / mol w .

[0512] An important determining parameter of polymer (D1) is its relative solubility number (RSN) determined according to the method described by J. Wu, Y. Xu, T. Dabros and H. Hamza, Colloids and Surface A: Physicochem Eng. Aspects 232 (2004) 229-237.

[0513] Water was added to 30 ml of a solvent mixture consisting of toluene and ethylene glycol dimethyl ether (EGDE) in a ratio of 2.6:97.4 (wherein 1 g of the (D1) sample was present as a clear solution) until a persistent turbidity appeared.

[0514] The relative solubility degree of compound (D1) is preferably between 4 ml and 50 ml, especially between 5 ml and 35 ml

[0515] Compared with the disclosure of EP 1609843 A2, water separation is generally achieved at a lower level of compound (D1).

[0516] The alkoxylated monomer ethyleneimine, low molecular weight polyethyleneimine or polyethyleneimine (D1) is added to the fuel in an amount of 0.1 weight ppm to 100 weight ppm, preferably 0.5 weight ppm to 50 weight ppm and more preferably 1 weight ppm to 10 weight ppm.

[0517] They can be used as such or dissolved or dispersed in a solvent, such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene, naphtha, diesel, heating oil, isoparaffins or commercial solvent mixtures such as Solvent Naphtha, AB, 150, 200, and Type D, preferably naphthalene-poor quality. In addition, long-chain alcohols (preferably alkanols having 6 or more, preferably 8 to 20 carbon atoms) can be used as solvents. Preferred examples are 2-ethylhexanol or 2-propylheptanol. They are preferably dissolved in fuel oils of animal or vegetable origin based on fatty acid alkyl esters. The additive of the present invention preferably contains 1% to 80%, especially 10% to 70%, particularly 25% to 60% of the solvent.

[0518] The polymer (D1) can be added to the fuel to which or to which is to be added according to the methods disclosed in the prior art. When more than one compound (D1) is to be used, these components can be introduced into the fuel together or separately in any combination.

[0519] Alkylphenolic resin (D2)

[0520] Component (D2) of the mixture according to the invention is at least one alkylphenol-formaldehyde resin having a repeating structural unit of formula (VI)

[0521]

[0522] wherein

[0523] R 41 is hydrogen or the group –[–X i –]] s –H

[0524] R 42 is a straight-chain or branched C4 to C 24 alkyl group

[0525] R 43 is hydrogen or a C1 to C4 alkyl group,

[0526] X i has the above meaning,

[0527] z is a positive integer from 10 to 80, preferably from 15 to 75, more preferably from 20 to 70 and especially from 25 to 65, and

[0528] s is a positive integer from 3 to 30, preferably from 5 to 10.

[0529] Alkylphenol-formaldehyde resins are in principle known and are described, for example, in the "Römpp Chemie Lexikon"( Chemie Lexikon), 9th edition, Thieme Verlag 1988 - 92, volume 4, pages 3351 et seq.

[0530] The alkyl or alkenyl group of the alkylphenol has 4 to 24, preferably 6 to 24, more preferably 8 to 22, especially 9 to 18 carbon atoms. They can be straight-chain or preferably branched, in which case the branches can contain secondary and tertiary structural units. The alkyl or alkenyl group is preferably n-hexyl and iso-hexyl, n-octyl and iso-octyl, n-nonyl and iso-nonyl, n-decyl and iso-decyl, n-dodecyl and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and tripropenyl, tetrapropenyl, pentapropenyl and polyisobutenyl groups up to C 24 The alkylphenol-formaldehyde resin can also contain up to 20 mol% of phenolic units and / or alkylphenols with short alkyl chains, such as butylphenol. For the alkylphenol-formaldehyde resin, the same or different alkylphenols can be used.

[0531] The aldehyde in the alkylphenol-formaldehyde resin has 1 to 10, preferably 1 to 4 carbon atoms and can carry additional functional groups. It is preferably an aliphatic aldehyde, more preferably formaldehyde or acetaldehyde, even more preferably formaldehyde.

[0532] The number-average molecular weight Mn of the alkylphenol-formaldehyde resin is preferably from 1000 g / mol to 50000 g / mol, especially from 5000 g / mol to 15000 g / mol. This preferably corresponds to a degree of condensation z of 10 to 80, preferably 15 to 75, more preferably 20 to 70 and especially 25 to 65.

[0533] Alkylphenol - formaldehyde resins are prepared in a known manner by alkaline catalysis to form a novolac - type condensation product or by acid catalysis to form a linear phenolic varnish - type condensation product.

[0534] The condensates obtained in both ways are suitable for the compositions of the present invention. Preferably, the condensation is carried out in the presence of an acid catalyst. To prepare the alkylphenol - formaldehyde resin, an alkylphenol having 6 to 24, preferably 8 to 22, especially 9 to 18 carbon atoms in each alkyl group or a mixture thereof and at least one aldehyde are reacted with each other, and about 0.5 mol to 2 mol, preferably 0.7 mol to 1.3 mol, especially equimolar amounts of aldehyde are used per mol of the alkylphenol compound.

[0535] Suitable alkylphenols are especially n - hexylphenol and iso - hexylphenol, n - octylphenol and iso - octylphenol, n - nonylphenol and iso - nonylphenol, n - decylphenol and iso - decylphenol, n - dodecylphenol and iso - dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, triallylphenol, tetraallylphenol and poly(isobutenyl)phenols up to C 24 of.

[0536] The alkylphenol is preferably para - substituted. The alkylphenol may carry one or more alkyl groups. It is preferably substituted by more than one alkyl group to an extent of up to 5 mol%, especially up to 20 mol% and particularly up to 40 mol%. Preferably up to 40 mol%, especially up to 20 mol% of the alkylphenol used is alkyl - substituted in the ortho - position. The alkylphenol is especially not substituted by a tertiary alkyl group in the ortho - position to the hydroxy group.

[0537] The aldehyde may be a mono - aldehyde or a di - aldehyde and carry additional functional groups such as - COOH. Particularly suitable aldehydes are formaldehyde, acetaldehyde, butyraldehyde, glutaraldehyde and glyoxylic acid, and preferably formaldehyde. Formaldehyde may be used in the form of paraformaldehyde or preferably in the form of an aqueous formalin solution of 20 wt% to 40 wt%. The corresponding amount of trioxane may also be used.

[0538] The reaction of the alkylphenol and the aldehyde is usually carried out in the presence of a basic catalyst (such as an alkali metal hydroxide or an alkylamine) or an acid catalyst (such as an inorganic acid or an organic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamic acid or haloacetic acid) and in the presence of an organic solvent (such as toluene, xylene, higher aromatic compounds or a mixture thereof) that forms an azeotrope with water. The reaction mixture is heated to a temperature of 90 to 200 °C, preferably 100 to 160 °C, and the water formed in the reaction is removed by azeotropic distillation during the reaction.

[0539] Solvents that do not release any protons under the condensation conditions can remain in the product after the condensation reaction. The resin can be used directly or after neutralizing the catalyst, and optionally also after further diluting the solution with an aliphatic and / or aromatic hydrocarbon or hydrocarbon mixture, such as a gasoline fraction, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as Naphtha, AB, iSO, 200, and type D.

[0540] Component (D2) does not necessarily need to be obtained from the reaction of a phenol with an aldehyde, and can also be obtained from the reaction of acetylene with a corresponding alkylphenol. In this case, in formula (VI), R 43 is methyl. Preferred examples of such resins are a resin sold by BASF and obtainable by reacting acetylene with p-tert-butylphenol.

[0541] The alkylphenol and aldehyde resins can be alkoxylated with: ethylene oxide, propylene oxide, 1-epoxybutane, 2-epoxybutane and / or epoxyisobutane, preferably ethylene oxide, propylene oxide and / or 1-epoxybutane, more preferably ethylene oxide and / or propylene oxide, as described in the prior art.

[0542] The amount of alkoxylate groups in component (D2) is from 10 wt% to 75 wt%.

[0543] Alkyl-, aryl-, or alkylaryl sulfonate or sulfate (D3)

[0544] In a preferred embodiment, the composition according to the invention further comprises at least one alkyl-, aryl- or alkylaryl sulfonate or sulfate (D3), preferably a sulfonate, more preferably an alkyl sulfonate or an alkylaryl sulfonate, and especially an alkylaryl sulfonate.

[0545] The alkyl group contains, for example, 6 to 24, preferably 8 to 20, more preferably 10 to 18 carbon atoms and can be straight-chain or branched.

[0546] Examples are n-hexyl and isohexyl, n-octyl and isooctyl, 2-ethylhexyl, n-nonyl and isononyl, n-decyl and isodecyl, 2-propylheptyl, n-dodecyl and isododecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and polyisobutenyl groups of tripropylene, tetrapropylene, pentapropylene and up to C 24 of.

[0547] The aryl group contains 6 to 12 carbon atoms.

[0548] Examples are phenyl or naphthyl.

[0549] The alkylaryl group contains, for example, from 7 to 30 carbon atoms, preferably from 10 to 24, more preferably from 14 to 22 carbon atoms.

[0550] Examples are n-hexylphenyl and iso-hexylphenyl, n-octylphenyl and iso-octylphenyl, 2-ethylhexylphenyl, n-nonylphenyl and iso-nonylphenyl, n-decylphenyl and iso-decylphenyl, 2-propylheptylphenyl, n-dodecylphenyl and iso-dodecylphenyl, tetradecylphenyl, hexadecylphenyl and octadecylphenyl.

[0551] The alkyl substituents are preferably mainly in the para position of the aromatic ring.

[0552] The counterions of the sulfate or sulfonate can be sodium ions, potassium ions, ammonium or magnesium ions, preferably sodium or potassium ions, and very preferably sodium ions.

[0553] Preferred sulfates are sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium dodecyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate and mixtures thereof.

[0554] Preferred sulfonates are sodium n-decylbenzenesulfonate, sodium iso-decylbenzenesulfonate, sodium n-dodecylbenzenesulfonate, sodium iso-dodecylbenzenesulfonate, sodium n-tetradecylbenzenesulfonate, sodium iso-tetradecylbenzenesulfonate and mixtures thereof, in particular sodium n-alkyl (C 10 -C 13 ) benzenesulfonate or sodium secondary alkyl (C 10 -C 13 ) benzenesulfonate.

[0555] Friction modifier (F)

[0556] At least one friction modifier (F) comprises:

[0557] --(F1) the propoxylated and / or butoxylated reaction product of (a) one or more fatty acids and (b) a dialkanolamine

[0558] and / or

[0559] --(F2) an amide of a polyalkyleneamine and a carboxylic acid

[0560] and / or

[0561] --(F3) at least one aliphatic monocarboxylic acid having from 12 to 30 carbon atoms,

[0562] and / or

[0563] --(F4) the reaction product of (a) one or more fatty acids and (b) a dialkanolamine, and

[0564] and / or

[0565] --(F5) A mixture of the following components:

[0566] ---(F5a) An aliphatic saturated or unsaturated monocarboxylic acid having 12 to 24 carbon atoms or their dimeric or trimeric products, which may exist as free carboxylic acids and / or in the form of ammonium salts, amides, esters, and / or nitriles, and

[0567] ---(F5b) A polycyclic hydrocarbon compound, which can be obtained from the distillation residue of natural oils that have been extracted from tree resins.

[0568] (F1) (a) One or more fatty acids and (b) propoxylated and / or butoxylated reaction product of dialkanolamine

[0569] Compound (F1) is the propoxylated and / or butoxylated reaction product of (a) one or more fatty acids, one or more fatty acid esters, or a mixture thereof, and (b) a dialkanolamine (such as diethanolamine).

[0570] More specifically, compound (F1) includes a propoxylated and / or butoxylated amide having the formula (I) and an ester compound of formula I(a):

[0571] (I) R 7 -C(=O)-N-[-CHR a CHR b -O-(-CHR 8 -CHR 9 -O) n H][-CHR a CHR b -O-(CHR 8 -CHR 9 -O) m -H|

[0572] (Ia) R 7 -C(=O)-O-CHR a CHR b -N-[-CHR a CHR b O-(CHR 8 CHR 9 -O) q -H][-(CHR 8 CHR 9 -O) p -H]

[0573] wherein R 7 is a straight-chain or branched-chain, saturated or unsaturated C7-C 23 aliphatic hydrocarbon group, optionally containing at least one hydroxyl group;

[0574] R a and R b are each hydrogen, or one of R a and R b is hydrogen and the other of R a and R b is methyl;

[0575] -CHR 8 -CHR 9 -O is independently -CH2-CH(CH3)-O, -CH2-CH(C2H5)-O, -CH(CH3)-CH2-O or -CH(C2H5)-CH2-O

[0576] n + m is from 0.5 to 5, where n and m may be the same or different, and one of n and m may be 0; and p + q is from 0 to 5, where p and q may be the same or different, and q alone may be 0, or both p and q may be 0.

[0577] In a preferred embodiment, p + q is from 0 to 3, more preferably p is from 0 to 3 and q is 0, and most preferably p is from 1 to 3 and q is 0.

[0578] In some embodiments, the amide is propoxylated, i.e., one of R 2 and R 3 is hydrogen and the other is methyl. In other embodiments, the amide is butoxylated, i.e., one of R 2 and R 3 is hydrogen and the other is ethyl. In still further embodiments, the amide is propoxylated and butoxylated. In a preferred embodiment, n + m is from 1 to 5, and more preferably from 1 to 3.

[0579] Another aspect of the present invention is to provide a method for improving the fuel economy of an internal combustion engine, the method comprising adding an amide of formula (I) and an ester of formula (Ia) to a hydrocarbon fuel and using the resulting fuel in an internal combustion engine.

[0580] More specifically, the propoxylated / butoxylated amides and esters of the present invention of formulae (I) and (Ia) are prepared by first reacting at least one fatty acid and / or at least one fatty acid ester with a dialkanolamine to form a dialkanolamide and an ester. The dialkanolamide and ester are then propoxylated and / or butoxylated using from one to five moles of propylene oxide and / or butylene oxide. The dialkanolamide and ester are not alkoxylated with ethylene oxide. The major product is the amide of formula (I), with the ester of formula (Ia) being present in an amount of at most 30%, more particularly from about 0.1% to about 30%, based on the total weight of the amide (I) and the ester (Ia).

[0581] More specifically, the fatty acid and / or fatty acid ester used in the reaction for forming the amide contains 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 18 carbon atoms. Thus, the fatty acid and / or fatty acid ester can be, but is not limited to, lauric acid, myristic acid, palmitic acid, stearic acid, caprylic acid, pelargonic acid, behenic acid, cerotic acid, montanic acid, lignoceric acid, nonadecenoic acid, erucic acid, linoleic acid, erythroanic acid, linolenic acid, arachidonic acid, chypanυdoic acid, ricinoleic acid, ceroplastic acid, capric acid, isostearic acid, gadoleic acid, myristoleic acid, palmitoleic acid, linderic acid, oleic acid, umbellulic acid, their esters, and their mixtures.

[0582] The fatty acid / fatty acid ester can also be derived from vegetable oils or animal oils, such as, but not limited to, coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, castor oil, peanut oil, jojoba oil, soybean oil, sunflower oil, walnut oil, sesame seed oil, rapeseed oil, colza oil, beef tallow, lard, blubber, seal oil, dolphin oil, cod liver oil, corn oil, tall oil, cottonseed oil, and their mixtures. Vegetable oils contain a mixture of fatty acids. For example, coconut oil typically contains the following fatty acids: caprylic acid (8%), capric acid (7%), lauric acid (48%), myristic acid (17.5%), palmitic acid (8.2%), stearic acid (2%), oleic acid (6%), and linoleic acid (2.5%).

[0583] The fatty acid component of the amide of formula (II) and the ester of formula (IIa) can also be derived from fatty acid esters, such as, for example, trilaurin, tristearin, tripalmitin, dilaurin, monostearin, ethylene glycol dilaurate, pentaerythritol tetrastearate, pentaerythritol trilaurate, sorbitan monopalmitate, sorbitan pentastearate, propylene glycol monostearate, and their mixtures.

[0584] The fatty acid component comprises one or more fatty acids themselves, one or more fatty acid methyl esters, one or more fatty acid ethyl esters, one or more vegetable oils, one or more animal oils, and their mixtures. The amide produced by the reaction can contain by-products such as glycerol, ethylene glycol, sorbitol, and other polyhydroxy compounds. If desired, the water, methanol, and ethanol by-products from these embodiments are readily removed from the reaction to substantially reduce the amount of unwanted by-products. The by-product polyhydroxy compounds do not adversely affect the final propoxylated / butoxylated amide (I) and are generally allowed to remain in the reaction mixture.

[0585] Preferred fatty acid / fatty acid esters include lauric acid, or a compound having a lauric acid residue, such as coconut oil.

[0586] React fatty acids and / or fatty acid esters with dialkanolamines to obtain dialkanolamides (II). The dialkanolamines contain hydrogen atoms for reacting with the carboxyl or ester groups of the fatty acids or fatty acid esters. The dialkanolamines also contain two hydroxyl groups for subsequent reaction with propylene oxide and / or butylene oxide. A portion of the dialkanolamine reacts with the fatty acids and / or fatty acid esters to obtain an ester (IIa) through the reaction of the hydroxyl groups of the dialkanolamine with the fatty acids and / or fatty acid esters. The amino groups can be used for subsequent reaction with propylene oxide and / or butylene oxide to form alkoxylated esters (Ia).

[0587] Preferred dialkanolamines contain two or three carbons in each of the two alkanol groups. Thus, preferred dialkanolamines include diethanolamine, diisopropylamine, and di-n-propylamine. The most preferred dialkanolamine is diethanolamine.

[0588] In the preparation of the amides (II) and esters (IIa), the dialkanolamine can be present in an equimolar amount with the fatty acid residues in the fatty acids or fatty acid esters. In another embodiment, the dialkanolamine is present in a molar amount different from the number of moles of fatty acid residues, i.e., a molar excess or deficiency. In a preferred method, the number of moles of the dialkanolamine is substantially equal to the number of moles of fatty acid residues.

[0589] As used herein, the term "fatty acid residue" is defined as R 7 -C(=O). Thus, the methyl ester of a fatty acid (i.e., R 7 -C(=O)OCH3) contains one fatty acid residue, and the preferred method utilizes a dialkanolamine in substantially equimolar amounts with the methyl ester. Triglycerides contain three fatty acid residues, and the preferred method utilizes about three moles of dialkanolamine per mole of triglyceride.

[0590] Generally, the molar ratio of dialkanolamine to fatty acid residue is from about 0.3 moles to about 1.5 moles, preferably from about 0.6 moles to about 1.3 moles, and more preferably from about 0.8 moles to about 1.2 moles of dialkanolamine per mole of fatty acid residue. To achieve all the advantages of the present invention, the molar ratio of dialkanolamine to fatty acid residue is from about 0.9 moles to about 1.1 moles per mole of fatty acid residue.

[0591] The reaction for preparing the amides (II) and esters (IIa) can be carried out in the presence or absence of a catalyst. Generally, a basic catalyst is employed. More specifically, the catalyst can be an alkali metal alkoxide, such as sodium methoxide, sodium ethoxide, potassium methoxide, or potassium ethoxide. Alkali metal hydroxides (such as sodium hydroxide or potassium hydroxide) and alkali metal carbonates (such as sodium carbonate or potassium carbonate) can also be used as catalysts.

[0592] The amount of catalyst (if present) is generally from about 0.01% to about 5% by weight relative to the amount of amide (II) and ester (IIa) to be produced. The reaction temperature for forming amide (II) and ester (IIa) is generally from about 50 °C to about 200 °C. The reaction temperature is generally higher than the boiling point of the alcohol (e.g., methanol) and / or water produced during the reaction to remove the water and / or alcohol produced in the reaction. Generally, the reaction is carried out for about 2 to about 24 hours.

[0593] The propoxylation / butoxylation reaction is generally carried out under basic conditions, for example by employing a basic catalyst of the type used in the preparation of amide (II) and ester (IIa). Additional basic catalysts are nitrogen-containing catalysts such as imidazole, N,N-dimethylethanolamine, and N,N-dimethylbenzylamine. The alkoxylation reaction can also be carried out in the presence of a Lewis acid such as titanium trichloride or boron trifluoride.

[0594] Based on the total amount of amide (II) and ester (IIa) used in the alkoxylation reaction, the amount of catalyst used is from about 0.5% to about 0.7% by weight. In some embodiments, the catalyst is omitted.

[0595] The temperature of the alkoxylation reaction is generally from about 80 °C to about 180 °C. Preferably, the alkoxylation reaction is carried out under an atmosphere (e.g., nitrogen) that is inert under the reaction conditions.

[0596] The alkoxylation reaction can also be carried out in the presence of a solvent. The solvent is inert under the reaction conditions. Suitable solvents are aromatic or aliphatic hydrocarbon solvents such as hexane, toluene, and xylene. Halogenated solvents such as chloroform or ether solvents such as dibutyl ether and tetrahydrofuran can also be used.

[0597] In a preferred embodiment, the reaction mixture that produces dialkanolamide (II) and ester (IIa) is used in the alkoxylation reaction without purification to provide alkoxylated amide (I) and alkoxylated ester (Ia). In another preferred embodiment, the reaction mixture that provides alkoxylated amide (I) and ester (Ia) is also used without purification. Thus, the preferred reaction products of the present invention include a variety of products, including for example alkoxylated amide (I), alkoxylated ester (Ia), dialkanolamide (II), ester (IIa), unreacted dialkanolamine, by-product hydroxy compounds (e.g., glycerol or other alcohols), mono- and / or di-esters of the starting triglyceride, polyalkylene oxide oligomers, amino esters, and ester-amides.

[0598] More details regarding the method for preparing the compound can be found in WO 2010 / 005720.

[0599] (F2) Amide of polyalkyleneamine and carboxylic acid

[0600] The amide (F2) has the formula (III):

[0601] R 10 -(C=O)-(NR 11 )-R 12

[0602] where

[0603] R 10 is a straight-chain or branched-chain, preferably branched-chain C7 to C 29 alkyl or C7 to C 29 alkenyl, preferably C7 to C 23 alkyl or C7 to C 23 alkenyl

[0604] R 11 is hydrogen or C1 to C4 alkyl, and

[0605] R 12 is a hydrocarbon residue containing 12 to 200 carbon atoms obtainable by the polymerization of olefins.

[0606] The amide of formula (III) can be obtained from the carboxylic acid R 10 -COOH or its derivatives and the amine R 12 -NHR 11 preferably from the carboxylic acid R 10 -COOH or its derivatives and the amine R 12 -NHR 11 where R 10 、R 11 and R 12 are as defined below.

[0607] The derivatives of the carboxylic acid are:[[]]

[0608] - its alkyl esters, preferably C1 to C4 alkyl esters, more preferably methyl or ethyl esters, and most preferably the methyl ester,

[0609] - its acid anhydrides or

[0610] - its chlorides.

[0611] The preferred derivative of the carboxylic acid is the alkyl ester.

[0612] The substituent R 10 is C7 to C 29 alkyl or C7 to C 29 alkenyl, preferably C7 to C 23 alkyl or C7 to C 23 alkenyl, more preferably C7 to C 17 alkyl or C7 to C 17 alkenyl.

[0613] The carboxylic acid R 10Examples of -COOH are caprylic acid (octanoic acid), 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, pelargonic acid, isononanoic acid, 2-propylheptanoic acid, capric acid (decanoic acid), undecanoic acid, lauric acid (dodecanoic acid), tridecanoic acid, myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), margaric acid, stearic acid (octadecanoic acid), isostearic acid, oleic acid, linoleic acid, trans-linoleic acid, erucic acid, arachidic acid, behenic acid, lignoceric acid, and cerotic acid. The above monocarboxylic acids (including the so-called fatty acids) can be of synthetic or natural origin. Mixtures of the above aliphatic monocarboxylic acids can also be used.

[0614] In one embodiment of the present invention, part of R 10 is a branched alkyl residue.

[0615] In one embodiment, the carboxylic acid R 10 -COOH is isononanoic acid.

[0616] As used herein, isononanoic acid refers to one or more branched aliphatic carboxylic acids having 9 carbon atoms. Embodiments of isononanoic acid can include 7-methyloctanoic acid (e.g., CAS Nos. 693-19-6 and 26896-18-4), 6,6-dimethylheptanoic acid (e.g., CAS No. 15898-92-7), 3,5,5-trimethylhexanoic acid (e.g., CAS No. 3302-10-1), 3,4,5-trimethylhexanoic acid, 2,5,5-trimethylhexanoic acid, 2,2,4,4-tetramethylpentanoic acid (e.g., CAS No. 3302-12-3), and combinations thereof. In a preferred embodiment, isononanoic acid has greater than 90% of one of 7-methyloctanoic acid, 6,6-dimethylheptanoic acid, 3,5,5-trimethylhexanoic acid, 3,4,5-trimethylhexanoic acid, 2,5,5-trimethylhexanoic acid, and 2,2,4,4-tetramethylpentanoic acid as its main component. The balance of isononanoic acid can include other nine-carbon carboxylic acid isomers and small amounts of one or more contaminants. In a preferred embodiment, isononanoic acid has greater than 90% of 3,5,5-trimethylhexanoic acid as its main component, and even more preferably, the main component is greater than 95% of 3,5,5-trimethylhexanoic acid.

[0617] In a preferred embodiment, the carboxylic acid R 10 -COOH is a fatty acid or a mixture of fatty acids containing 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms.

[0618] Such fatty acid mixtures can be derived from natural sources, for example from vegetable oils such as 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 that can be obtained from wheat, jute, sesame and shea butter; peanut oil, jatropha oil and linseed oil can also be used. The extraction of these oils and their conversion to fatty acids are known in the prior art or can be deduced therefrom.

[0619] Such fatty acid mixtures especially include caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, elaidic acid and linoleic acid or mixtures thereof.

[0620] For R 11 = H, the polyalkyleneamine is as described above under (A1) and can be the same as or different from (A1).

[0621] Preferably, they are the same as in (A1).

[0622] In the amine R 12 -NHR 11 the residue R 11 is hydrogen or a C1 to C4 alkyl group, preferably hydrogen or methyl, and more preferably hydrogen.

[0623] The residue R 12 is a hydrocarbon residue containing 12 to 200, preferably 16 to 150, more preferably 20 to 100, even more preferably 30 to 90 and especially 40 to 80 carbon atoms, which can be obtained by polymerization of olefins, preferably by polymerization of an olefin mixture containing propylene, 1-butene or isobutene, more preferably by propylene or isobutene, and most preferably by isobutene.

[0624] In one embodiment, the polyolefin from which the residue R 12 is based is derived from an olefin polymer as described above under (A1). The olefin polymer can include homopolymers and copolymers of polymerizable olefin monomers having 2 to about 16 carbon atoms, 2 to about 6 carbon atoms or 2 to about 4 carbon atoms.

[0625] Preferably, in the amine R 12 -NHR 11 the residue R 11 is hydrogen and the residue R 12 is derived from a polyisobutene having a number average molecular weight Mn of 168 to 2300, more preferably 224 to 1500, even more preferably 550 to 1300, most preferably 700 to 1300 and especially 950 to 1050.

[0626] In a preferred embodiment, these amines can be obtained by oligomerizing propylene, isobutene, 1-butene or 2-butene, preferably propylene or isobutene, especially isobutene, to form a mixture of oligomers or polymers containing double bonds, followed by hydroformylation and reductive amination with ammonia.

[0627] The description of this embodiment under (A1) above applies here.

[0628] Such polyisobutenamines are commercially available under the trade name KEROCOM(R) PIBA from BASF SE, Ludwigshafen.

[0629] The idealized structure of such polyisobutenamines is

[0630] For a number-average molecular weight Mn of the base polyisobutene from 168 to 2300, x is from 1 to 39; for a Mn of 224 to 1500, x is from 2 to 25; for a Mn of 550 to 1300, x is from 8 to 21; for a Mn of 700 to 1300, x is from 10 to 21; and for a Mn of 950 to 1050, x is from 15 to 17.

[0631] If the base polyisobutene is prepared from an isobutene-containing C4 hydrocarbon stream (see above) that contains monomers other than isobutene, the polymer backbone contains other monomers in polymerized form, such as 1-butene and cis- and trans-2-butene, especially 1-butene.

[0632] The preparation of such amides is described, for example, in WO 2022 / 263254 A1.

[0633] (F3) – Fatty acid

[0634] The fatty acid (F3) is at least one aliphatic monocarboxylic acid having 12 to 30 carbon atoms, preferably having 14 to 26 carbon atoms, very preferably having 16 to 24 carbon atoms and especially having 18 to 20 carbon atoms.

[0635] The monocarboxylic acid can be saturated or mono-, di- or polyunsaturated, preferably unsaturated, very preferably monounsaturated.

[0636] Mixtures of aliphatic monocarboxylic acids can also be used, especially from natural and renewable sources, such as animal oils or preferably vegetable oils. Such mixtures of aliphatic monocarboxylic acids are usually obtained by saponification of natural oils and, depending on the source and origin of the natural oil, yield mixtures of aliphatic monocarboxylic acids having different numbers of carbon atoms. Preferred are linseed oil, coconut fat, palm kernel oil, palm oil, soybean oil, peanut oil, cocoa butter, shea butter, cottonseed oil, corn oil, sunflower oil, rapeseed oil or castor oil.

[0637] Examples of aliphatic monocarboxylic acids are dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid, trans-linoleic acid, erucic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid, preferably tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid, trans-linoleic acid, erucic acid, arachidic acid and behenic acid, very preferably hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid and trans-linoleic acid, and especially oleic acid, linoleic acid and trans-linoleic acid. Oleic acid is particularly preferred.

[0638] (F4) (a) One or more fatty acids and (b) reaction product of dialkanolamine

[0639] Compound (F4) is a reaction product of (a) one or more fatty acids, one or more fatty acid esters or a mixture thereof and (b) a dialkanolamine such as diethanolamine.

[0640] More specifically, compound (F4) comprises an amide having the formula (I) and an ester compound having the formula (Ia), as outlined above for compound (F1), with the difference that the amide and the ester are not alkoxylated, i.e., n, m, p and q are 0 (zero):

[0641] (Ic)R 7 -C(=O)-N-[-CHR a CHR b -O-H]2

[0642] (Id)R 7 -C(=O)-O-CHR a CHR b -NH-CHR a CHR b -O-H

[0643] wherein R 7 is a straight-chain or branched-chain, saturated or unsaturated C7-C 23 aliphatic hydrocarbon group, optionally containing at least one hydroxyl group;

[0644] R a and R b are both hydrogen, or one of R a and R b is hydrogen and the other of R a and R b is methyl.

[0645] Another aspect of the present invention is to provide a method for improving the fuel economy of an internal combustion engine, the method comprising adding an amide of formula (Ic) and an ester of formula (Id) to a hydrocarbon fuel and using the resulting fuel in an internal combustion engine.

[0646] More specifically, the amides and esters of structural formulas (Ic) and (Id) are prepared by reacting at least one fatty acid and / or at least one fatty acid ester with a dialkanolamine to form a dialkanolamide (Ic) and an ester (Id). The main product is the amide of formula (Ic), wherein the ester of formula (Id) is present in an amount of at most 30%, more particularly from about 0.1% to about 30%, based on the total weight of the amide (Ic) and the ester (Id).

[0647] More specifically, the fatty acid and / or fatty acid ester used in the reaction for forming the amide contains 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 18 carbon atoms. Thus the fatty acid and / or fatty acid ester can be, but is not limited to, lauric acid, myristic acid, palmitic acid, stearic acid, caprylic acid, pelargonic acid, behenic acid, cerotic acid, montanic acid, lignoceric acid, nonadecenoic acid, erucic acid, linoleic acid, erythroanic acid, linolenic acid, arachidonic acid, chypanυdoic acid, ricinoleic acid, ceroplastic acid, capric acid, isostearic acid, gadoleic acid, myristoleic acid, palmitoleic acid, linderic acid, oleic acid, umbellulic acid, their esters and their mixtures.

[0648] The fatty acid / fatty acid ester can also be derived from vegetable oils or animal oils, such as, but not limited to, coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, castor oil, peanut oil, jojoba oil, soybean oil, sunflower oil, walnut oil, sesame seed oil, rapeseed oil, colza oil, beef tallow, lard, blubber, seal oil, dolphin oil, cod liver oil, corn oil, tall oil, cottonseed oil and mixtures thereof. Vegetable oils contain mixtures of fatty acids. For example, coconut oil typically contains the following fatty acids: caprylic acid (8%), capric acid (7%), lauric acid (48%), myristic acid (17.5%), palmitic acid (8.2%), stearic acid (2%), oleic acid (6%) and linoleic acid (2.5%).

[0649] The fatty acid component of the amide of formula (Ic) and the ester of formula (Id) can also be derived from fatty acid esters such as, for example, trilaurin, tristearin, tripalmitin, dilaurin, monostearin, ethylene glycol dilaurate, pentaerythritol tetrastearate, pentaerythritol trilaurate, sorbitan monopalmitate, sorbitan pentastearate, propylene glycol monostearate and mixtures thereof.

[0650] The fatty acid component comprises one or more fatty acids per se, one or more fatty acid methyl esters, one or more fatty acid ethyl esters, one or more vegetable oils, one or more animal oils, and mixtures thereof. The amides produced by the reaction may contain by-products such as glycerol, ethylene glycol, sorbitol, and other polyhydroxy compounds. If desired, the water, methanol, and ethanol by-products from these embodiments are readily removed from the reaction to substantially reduce the amount of unwanted by-products. The by-product polyhydroxy compounds do not adversely affect the final reaction mixture and are generally allowed to remain in the reaction mixture.

[0651] Preferred fatty acids / fatty acid esters include isostearic acid.

[0652] Reacting a fatty acid and / or a fatty acid ester with a dialkanolamine gives a dialkanolamide (Ic) or an ester (Id). The dialkanolamine contains hydrogen atoms for reacting with the carboxyl or ester group of the fatty acid or fatty acid ester. A portion of the dialkanolamine reacts with the fatty acid and / or fatty acid ester to give an ester (Id) by reaction of the hydroxyl group of the dialkanolamine with the fatty acid and / or fatty acid ester.

[0653] Preferred dialkanolamines contain two or three carbons in each of the two alkanol groups. Thus, preferred dialkanolamines include diethanolamine, diisopropylamine, and dipropylamine. The most preferred dialkanolamine is diethanolamine.

[0654] In the preparation of the amide (Ic) and the ester (Id), the dialkanolamine may be present in an equimolar amount with respect to the fatty acid residue in the fatty acid or fatty acid ester. In another embodiment, the dialkanolamine is present in a molar amount different from the number of moles of the fatty acid residue, i.e., a molar excess or deficiency. In a preferred method, the number of moles of the dialkanolamine is substantially equal to the number of moles of the fatty acid residue.

[0655] As used herein, the term "fatty acid residue" is defined as R 7 -C(=O). Thus, the methyl ester of a fatty acid (i.e., R 7 -C(=O)OCH3) contains one fatty acid residue, and the preferred method utilizes a dialkanolamine in substantially equimolar amounts with the methyl ester. A triglyceride contains three fatty acid residues, and the preferred method utilizes about three moles of dialkanolamine per mole of triglyceride.

[0656] Typically, the molar ratio of dialkanolamine to fatty acid residue is from about 0.3 moles to about 1.5 moles, preferably from about 0.6 moles to about 1.3 moles, and more preferably from about 0.8 moles to about 1.2 moles of dialkanolamine per mole of fatty acid residue. To achieve all of the advantages of the present invention, the molar ratio of dialkanolamine to fatty acid residue is from about 0.9 moles to about 1.1 moles per mole of fatty acid residue.

[0657] The reaction conditions for preparing the compound (F4) are as described above for the compound (F1).

[0658] (F5) (F5a) Mixture of aliphatic saturated or unsaturated monocarboxylic acid and (F5b) polycyclic hydrocarbon compound 。

[0659] Component (F5), which is suitable as a friction modifier, is a mixture of the following components:

[0660] --- (F5a) aliphatic saturated or unsaturated monocarboxylic acids having 12 to 24 carbon atoms or their dimeric or trimeric products, which may be present as the free carboxylic acid and / or in the form of ammonium salts, amides, esters, and / or nitriles, and

[0661] --- (F5b) polycyclic hydrocarbon compounds, which can be obtained from the distillation residues of natural oils that have been extracted from tree resins.

[0662] Component (F5a) in the mentioned mixture preferably comprises aliphatic saturated or unsaturated monocarboxylic acids having 14 to 20 carbon atoms, especially 16 to 18 carbon atoms. These monocarboxylic acids are usually straight-chain. For component (F5a), useful monocarboxylic acids are especially naturally occurring fatty acids, especially those having 14 to 20 carbon atoms, especially 16 to 18 carbon atoms. Typical representatives of such monocarboxylic acids or fatty acids are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and elaidic acid. Component (F5a) can consist of only one such monocarboxylic acid or fatty acid, or preferably of a mixture of two or more such monocarboxylic acids or fatty acids. Naturally occurring fatty acids obtained, for example, from rapeseed oil, soybean oil, or tall oil are usually mixtures of several such monocarboxylic acids.

[0663] Component (F5b), the natural source of which is tree resin, especially coniferous tree resin from pine or spruce, is formed from one or preferably several so-called resin acids. Resin acids are polycyclic hydrocarbon compounds containing a carboxyl group. As the most important representatives, they include abietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, neoabietic acid, longifolene acid, pimaric acid, isopimaric acid, and levopimaric acid. These resin acids can also be present partially in oxidized form, i.e., the so-called oxygenated acids.

[0664] In a preferred embodiment, components (F5a) and (F5b) are used in the mentioned mixture in a weight ratio of 65:35 to 99.9:0.1, especially 90:10 to 99.9:01, particularly 97:3 to 99.9:0.1.

[0665] Particularly suitable mixtures of components (F5a) and (F5b) are tall oil fatty acids and dimerized tall oil fatty acids. Tall oil fatty acids are prepared from tall oil, which is obtained by digesting resin-rich wood types, especially wood from spruce or pine. Tall oil fatty acids are a mixture of fatty acids in which C 18 unsaturated monocarboxylic acids, especially oleic acid, linoleic acid and conjugated C 18 fatty acids as well as 5,9,12-octadecatrienoic acid predominate, in addition to resin acids and, if appropriate, oxygen-containing acids (i.e. oxidized fatty acids and resin acids). The resin acids form the so-called tall oil resin, in which mainly abietic acid, dehydroabietic acid and palustric acid are present, and in addition to further resin acids, small amounts of dihydroabietic acid, neoabietic acid, pimaric acid and isopimaric acid can also be detected. In the best quality tall oil fatty acids, the fatty acid fraction accounts for at least 97% by weight and the tall oil resin fraction at most 3% by weight.

[0666] The recovery of tall oil fatty acids and resin acids from tree resins by digestion, extraction and distillation methods is known to the person skilled in the art and therefore does not need to be explained in detail here.

[0667] In dimerized tall oil fatty acids, the fatty acid component (F5a) is present in dimerized form. The dimerization and trimerization of monocarboxylic acids or fatty acids can be carried out by methods conventionally used for this purpose and are in principle known to the person skilled in the art.

[0668] The monocarboxylic acids or fatty acids of component (F5a) and their dimerized or trimerized products can be present as free carboxylic acids and / or as ammonium salts (e.g. as NH4 salts or substituted ammonium salts such as mono-, di-, tri- or tetramethylammonium salts), and / or in the form of amides, esters and / or nitriles. Typical amide structures have -CO-NH2, -CO-NH-alkyl or -CO-N(alkyl)2 moieties, where "alkyl" here particularly denotes C1 to C4 alkyl, such as methyl or ethyl. Ester structures generally include C1 to C4 alkanol ester groups, such as methoxycarbonyl or ethoxycarbonyl groups.

[0669] Other additives

[0670] Typical other additives in the additive package or fuel according to the invention can be cloud point depressants, antioxidants, metal deactivators and solvents for the package.

[0671] Cloud point depressant

[0672] Suitable clouding agents are, for example, the alkali metal salts or alkaline earth metal salts of alkyl-substituted phenolsulfonic acids and naphthalenesulfonic acids and the alkali metal salts or alkaline earth metal salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates (e.g., alcohol ethoxylates), phenol alkoxylates (e.g., tert-butylphenol ethoxylates or tert-amylphenol ethoxylates), fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO) (e.g., including in the form of EO / PO block copolymers), polyethyleneimines or polysiloxanes.

[0673] Also suitable clouding agents are the EO / PO-based alkoxylates of alkylphenol-formaldehyde condensates (novolacs, resoles or calixarene types), diols (e.g., propylene glycol, ethylene glycol), triols (e.g., glycerol or trimethylolpropane), the EO / PO-based alkoxylates of ethylenediamine or polyethyleneimine. Also suitable clouding agents are alkylbenzenesulfonic acids, dialkyl sulfosuccinates or their alkali metal salts or ammonium salts. Suitable clouding agents are described in WO 96 / 22343. Also suitable diglycidyl ether-based clouding agents are described in US 3383326 and US 3511882.

[0674] Other suitable clouding agents are, for example, alkoxylated phenol-formaldehyde condensates, such as the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).

[0675] Antioxidant

[0676] Suitable antioxidants are, for example, substituted phenols, such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-di-tert-butyl-6-methylphenol, preferably hindered phenols with an ester group in the para position, such as 3-[3,5-bis-(dimethyl ethyl)-4-hydroxy-phenyl]propionic acid C6 to C 20 alkyl esters, such as 2-ethylhexyl ester or stearyl ester, and phenylenediamines such as N,N'-di-sec-butyl-p-phenylenediamine.

[0677] Metal deactivator

[0678] Suitable metal deactivators are, for example, salicylic acid derivatives, such as N,N'-bis(salicylidene)-1,2-propanediamine.

[0679] Solvent

[0680] Suitable solvents are, for example, nonpolar organic solvents, such as aromatic and aliphatic hydrocarbons, for example toluene, xylene, white spirits and the products sold under the trade names SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), and 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 above-mentioned additives and co-additives, and they are intended to dissolve or dilute these additives and co-additives for better handling.

[0681] Composition

[0682] The methanol-containing fuel according to the present invention comprises the above-mentioned additive package in an amount such that the contents of the individual components in the final fuel are as follows:

[0683] (A) Sediment Control Agents

[0684] - (A1) in the case of polyalkyleneamines, in an amount of 10 to 1000 ppm by weight, preferably 25 to 500 ppm by weight, more preferably 50 to 250 ppm by weight,

[0685] - (A2) in the case of quaternary ammonium compounds as deposit control agents, they are generally present in the fuel in an amount of 10 to 100 ppm by weight, preferably 20 to 50 ppm by weight, more preferably 25 to 40 ppm by weight,

[0686] - (A3) in the case of polyetheramines, in an amount of 10 to 1000 ppm by weight, preferably 25 to 500 ppm by weight, more preferably 50 to 250 ppm by weight,

[0687] - (A4) in the case of Mannich compounds, in an amount of 10 to 1000 ppm by weight, preferably 25 to 500 ppm by weight, more preferably 50 to 250 ppm by weight,

[0688] - (A5) in the case of polyalkenyl succinimide, an amount of 10 to 1000 ppm by weight, preferably 25 to 500 ppm by weight, more preferably 50 to 250 ppm by weight,

[0689] - (A6) in the case of branched amines, an amount of 10 to 3000 ppm by weight, preferably 15 to 1000 ppm by weight, more preferably 20 to 500 ppm by weight, most preferably 25 to 250 ppm,

[0690] (B) A corrosion inhibitor in an amount of 0.1 to 10 ppm by weight, preferably 0.2 to 8 ppm by weight, more preferably 0.3 to 7 ppm by weight, most preferably 0.5 to 5 ppm by weight, and even 1 to 3 ppm by weight

[0691] (C) A carrier oil in an amount of 10 to 3000 ppm by weight, preferably 20 to 1000 ppm by weight, more preferably 50 to 700 ppm by weight, most preferably 70 to 500 ppm by weight

[0692] (D) A cloud point depressant in an amount of 0.5 to 100 ppm by weight, preferably 1 to 50 ppm by weight, more preferably 1.5 to 40 ppm by weight, most preferably 2 to 30 ppm by weight, such as 3 to 20 ppm by weight

[0693] (F) A friction modifier in an amount of 25 to 1000 ppm, preferably 50 to 500 ppm, more preferably 75 to 250 ppm

[0694] The above other additive components (if any) are each usually present in the gasoline fuel in an amount of 0.5 to 200 ppm by weight, preferably 1 to 100 ppm by weight, more preferably 1.5 to 40 ppm by weight, most preferably 2 to 30 ppm by weight.

[0695] The subject matter of the present invention also relates to a fuel additive concentrate (fuel additive package) suitable for methanol-containing gasoline fuels, which comprises:

[0696] (A) A deposit control agent: 10 to 70% by weight, preferably 15 to 60% by weight, more preferably 20 to 50% by weight

[0697] (B) A corrosion inhibitor: 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

[0698] (C) A carrier oil: 0 to 80% by weight, preferably 5 to 60% by weight, more preferably 10 to 40% by weight of at least one carrier oil

[0699] (D) A cloud point depressant: 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

[0700] (F) Friction modifier: 0.01 wt% to 40 wt%, preferably 0.05 wt% to 35 wt%, more preferably 1 wt% to 30 wt%, even more preferably 5 wt% to 25 wt%,

[0701] At least one solvent or diluent in an amount of 0 wt% to 80 wt%, preferably 5 wt% to 50 wt%, more preferably 10 wt% to 40 wt%, and

[0702] Each of the above other additive components (if any) in an amount of 0 wt% to 15 wt%, preferably 0.5 wt% to 10 wt%, more preferably 1 wt% to 8 wt%, most preferably 3 wt% to 7 wt%;

[0703] Provided that the sum of the components is always 100%.

[0704] Example

[0705] Example 1 – Comparison of solubility of polyisobutenylamine in methanol-containing fuel and ethanol-containing fuel

[0706] KEROCOM PIBA 03 (CAS No. 886464-29-5, commercially available from BASF SE, Ludwigshafen, having an amine value of 22 to 27 mg KOH / g, 65 wt% solution in hydrocarbon) was added to gasoline fuels containing 85 vol% ethanol (E85, Figure 1 ) and methanol (M85, Figure 2 ) respectively. The amount of polyisobutyleneamine was increased from 50 wt ppm to 500 wt ppm (M85), and from 100 wt ppm to 1000 wt ppm (E85).

[0707] As the amount of polyisobutyleneamine added to the fuel increased, an increase in turbidity was observed.

[0708] The turbidity of 50 ppm polyisobutyleneamine added to M85 was roughly equivalent to that of 500 ppm polyisobutyleneamine added to E85, indicating that the solubility of polyisobutyleneamine in methanol-containing fuels is low.

[0709] Example 2 – Comparison of solubility of fuel additive components in methanol-containing fuel

[0710] Typical components of gasoline fuel additives were added to methanol and methanol-containing fuels, and their solubility and stability were visually determined during a storage period of about 3 months at room temperature.

[0711] Fuel:

[0712] Methanol (pure, M100)

[0713] Gasoline fuel containing 95% by volume of methanol (M95)

[0714] Gasoline fuel containing 80% by volume of methanol (M80)

[0715] Additive components:

[0716] PIBA: KEROCOM PIBA 03 as in Example 1

[0717] Mannich: Mannich base as described in WO 2016 / 038127

[0718] Quat: N,N-dimethyl-N-hexadecylamine quaternized with propylene oxide and polyisobutylene succinic acid obtained from succinic acid and polyisobutylene (Mn about 1000 g / mol); 50% by weight in 2-ethylhexanol, Synthesis Example 6 according to WO 2014 / 195464

[0719] FM: Amide of polyisobutyleneamine and coconut fatty acid as a friction modifier, as described in WO 2022 / 263254, Synthesis Example 3

[0720]

[0721]

[0722] The following additive components were tested and there was no change in the clear visual appearance of any of the three fuels during the storage period:

[0723] · Propoxylated tridecanol derived from triisobutene (after hydroformylation and hydrogenation) as a carrier oil, 380 ppm

[0724] · Oleic acid, 35 ppm

[0725] · A mixture of 22% dimer fatty acid (C18 fatty acid), 7% trimer fatty acid (C18 fatty acid), 11% dodecenyl succinic acid, and 3% oleic acid in a ca. 50% solution in Solvent Naphtha as a corrosion inhibitor, 30 ppm

[0726] · Copolymer of maleic anhydride and C 20 to C 24 olefins hydrolyzed with water as a corrosion inhibitor, 30 ppm, according to Synthesis Example 2 of WO 15 / 114029

[0727] · p-alkylbenzenesulfonic acid with C 10 -C 13 alkyl groups as a corrosion inhibitor, in aromatic hydrocarbons and 2-ethylhexanol as a solvent mixture, 4 ppm

[0728] · 20% having C 10 -C 13 A mixture of p-alkylbenzenesulfonic acid (isopropylammonium salt) having an alkyl group, 13% oleoyl sarcosine, and 13% ethylene oxide / propylene oxide copolymer as a corrosion inhibitor, 2 ppm in an aromatic hydrocarbon as a solvent.

Claims

1. A fuel composition for a spark-ignition internal combustion engine, said fuel composition comprising a major amount of fuel, said fuel comprising: - 97 wt% to 0 wt% gasoline and - 3 wt% to 100 wt% methanol Said fuel composition further comprises a minor amount of at least one fuel additive package, said at least one fuel additive package comprising: - at least one deposit control agent (A) selected from the group consisting of: -- (A1) polyalkyleneamine and -- (A2) quaternary ammonium compound -- (A3) polyetheramine -- (A4) polyisobutylene-substituted Mannich compound -- (A5) polyalkenyl succinimide -- (A6) branched amine - at least one corrosion inhibitor (B) selected from the group consisting of: -- (B1) hydrolysis copolymer of olefin and carboxylic acid -- (B2) dimer fatty acid -- (B3) amide of aliphatic or aromatic carboxylic acid and primary or secondary amine with at least one additional functional group, said at least one additional functional group being selected from the group consisting of carboxylic acid group, sulfonic acid group and amino group - at least one carrier oil (C) selected from the group consisting of: -- polyolefin, -- polyester, -- polyalkoxylate, -- aliphatic polyether, -- aliphatic polyetheramine, -- polyether initiated with alkylphenol, -- polyetheramine initiated with alkylphenol, and -- carboxylic acid ester of long-chain alkanol, - at least one cloud point depressant (D) selected from the group consisting of: -- alkyl-substituted phenolsulfonate and naphthalenesulfonate, -- fatty acid, -- alcohol alkoxylate -- phenol, alkylphenol and their alkoxylates, -- phenolic resin and alkylphenolic resin, -- condensation product of ethylene oxide (EO) and propylene oxide (PO), -- polyethyleneimine, -- alkoxylated polyethyleneimine, and -- polysiloxane, - at least one friction modifier (F) selected from the group consisting of: -- (F1) the propoxylated and / or butoxylated reaction product of (a) one or more fatty acids and (b) dialkanolamine, and -- (F2) amide of polyalkyleneamine and carboxylic acid -- (F3) at least one aliphatic monocarboxylic acid having 12 to 30 carbon atoms, -- (F4) the reaction product of (a) one or more fatty acids and (b) dialkanolamine, and -- (F5) a mixture of the following components: --- (F5a) an aliphatic saturated or unsaturated monocarboxylic acid having 12 to 24 carbon atoms or its dimer or trimer product, which may exist as a free carboxylic acid and / or in the form of an ammonium salt, amide, ester and / or nitrile, and --- (F5b) a polycyclic hydrocarbon compound, said polycyclic hydrocarbon compound being obtainable from the distillation residue of natural oil that has been extracted from resin.

2. The fuel composition according to claim 1, wherein the polyalkyleneamine (A1) is polyisobutyleneamine where x is from 1 to 39.

3. The fuel composition according to claim 1, wherein the quaternary ammonium compound (A2) has the following formula: + NR 1 R 2 R 3 R 4 A - where A - represents an anion, preferably a carboxylate R 5 COO - or a carbonate R 5 O-COO - , and R 1 、R 2 、R 3 、R 4 and R 5 are, independently of one another, organic residues having from 1 to 100 carbon atoms, substituted or unsubstituted, preferably unsubstituted, straight-chain or branched alkyl, alkenyl or hydroxyalkyl residues having from 1 to 100, more preferably from 1 to 75, even more preferably from 1 to 30, most preferably from 1 to 25 and especially from 1 to 20 carbon atoms. R 5 It may also be a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 20, preferably 5 to 12 carbon atoms.

4. The fuel composition according to claim 1, wherein the quaternary ammonium compound (A2) has the following formula: where in this formula, R a and R b each independently represents C1–C 20 alkyl or hydroxy-C1 to C4 alkyl, preferably R a represents C1–C 20 alkyl, preferably ethyl, n-butyl, n-octyl, n-dodecyl, tetradecyl or hexadecyl, and R b represents hydroxy-C1 to C4 alkyl, preferably 2-hydroxypropyl, A - represents an anion, preferably a carboxylate R as defined above 5 COO - or a carbonate R 5 O-COO - , more preferably C 12 -C 100 alkyl and alkenyl succinic acids, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicoseneyl succinic acid and polyisobutenyl succinic acid.

5. The fuel composition according to claim 1, wherein the quaternary ammonium compound (A2) has the following formula: wherein in this formula, PIB represents a number-average molecular weight M n of a polyisobutenyl residue from 550 g / mol to 2300 g / mol, preferably from 650 g / mol to 1500 g / mol and more preferably from 750 g / mol to 1300 g / mol, and R represents a hydroxy-C1 to C4 alkyl group, preferably 2-hydroxypropyl.

6. The fuel composition according to claim 1, wherein the polyetheramine compound (A3) has the following formula: R 20 -O-[-X i -] n -NR 21 R 22 wherein R 20 is hydrogen, C2 to C 30 alkyl, preferably C8 to C 20 alkyl, more preferably C9 to C 15 alkyl, even more preferably C 11 to C 14 alkyl, and in particular C 13 alkyl, which may be straight-chain or branched, preferably branched, or an alkyl-substituted phenyl residue R 19 -C6H4-, where R 19 is a straight-chain or branched alkyl group having 8 to 22, preferably 9 to 17, more preferably 10 to 13 carbon atoms, R 21 and R 22 each independently is hydrogen, C1-C4 alkyl, N,N-bis(C1-C4 alkylamino)-C1-C4 alkyl or –[-CH2-CH2-NH-] m -H, n is from 10 to 40, preferably from 12 to 30, more preferably from 18 to 25, and even more preferably from 20 to 23, m is from 1 to 4, preferably from 1 to 3, more preferably 2 or 3, and For X where i = 1 to n i independently 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-, and most preferably selected from the group consisting of -CH2-CH2-O-, -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-, and in particular selected from the group consisting of -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-.

7. The fuel composition according to claim 1, wherein the polyisobutene-substituted Mannich compound (A4) has the following formula: or has the following formula: wherein R 30 is a hydrocarbon residue having a number-average molecular weight Mn of from 85 to 5000, preferably from 113 to 2500, more preferably from 550 to 1500 and most preferably from 750 to 1100, and in particular a polyisobutylene group of the aforementioned molecular weight, more preferably derived from a "reactive" polyisobutylene group, R 31 is hydrogen, methyl, ethyl, isopropyl, n-butyl, tert-butyl, but-2-yl or pentyl, preferably hydrogen or methyl, and more preferably methyl, or the group -CH2-NR 32 R 33 or the group -CH2-NH-R 34 -NR 32 R 33 , R 32 and R 33 are each independently a C1-C6 alkyl group, preferably a C1-C4 alkyl group, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, even more preferably methyl, ethyl or n-butyl, or R 32 and R 33 together with the nitrogen atom form a five- or six-membered ring, preferably a pyrrolidine, piperidine or morpholine ring, and R 34 is a divalent alkylene residue having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably selected from the group consisting of methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene and 1,6-hexylene, and in particular 1,2-ethylene or 1,3-propylene.

8. The fuel composition according to claim 1, wherein the polyalkenyl succinimide (A5) comprises the reaction product of (1) a reaction intermediate that yields a hydrocarbon dicarboxylic acid and (2) a nucleophilic reactant.

9. The fuel composition according to claim 1, wherein the branched alkylamine (A6) is a primary amine R 36 -NH2 having an alkyl group R 36 with 8 to 22, preferably 10 to 17, more preferably 13 carbon atoms, and the alkyl group has at least 1.0, preferably 1.0 to 8.0, more preferably 1.5 to 7.0 branches.

10. The fuel composition according to any one of the preceding claims, wherein the olefin-carboxylic acid copolymer (B1) is a copolymer obtainable by the following steps: - copolymerizing in a first reaction step (I): (B1a) at least one ethylenically unsaturated monocarboxylic acid or dicarboxylic acid or their derivatives, preferably a dicarboxylic acid, (B1b) at least one α-olefin having at least 12 up to and including 30 carbon atoms, (B1c) optionally at least one additional aliphatic or alicyclic olefin having at least 4 carbon atoms and different from (B1b), and (B1d) optionally one or more additional copolymerizable monomers different from monomers (B1a), (B1b) and (B1c), selected from the group consisting of: (B1da) vinyl esters, (B1db) vinyl ethers, (B1dc) (meth)acrylates of alcohols having at least 5 carbon atoms, (B1dd) allyl alcohol or its ethers, (B1de) N-vinyl compounds selected from the group consisting of: vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-vinyl lactams, (B1df) ethylenically unsaturated aromatic compounds, (B1dg) α,β-ethylenically unsaturated nitriles, (B1dh) (meth)acrylamides and (B1di) allylamine, subsequently - in a second optional reaction step (II), partially or completely hydrolyzing and / or saponifying the anhydride or carboxylic acid ester functional groups present in the copolymer obtained from (I), said second reaction step being carried out at least when the copolymer obtained from the reaction step (I) does not contain any free carboxylic acid functional groups.

11. The fuel composition according to any one of claims 1 to 9, wherein the compound (B2) is a dimer of an unsaturated monocarboxylic acid having 9 to 30 carbon atoms.

12. The fuel composition according to claim 11, wherein the unsaturated monocarboxylic acid is selected from the group consisting of: myristoleic acid, palmitoleic acid, abietic acid, oleic acid, elaidic acid, isolenic acid, linoleic acid, trans-linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.

13. The fuel composition according to any one of claims 1 to 9, wherein the compound (B3) is selected from the group consisting of oleoylsarcosine and the reaction product of naphthenic acid and diethylenetriamine.

14. The fuel composition according to any one of the preceding claims, wherein the carrier oil (C) is a 5 - to 30 - fold alkoxylated straight - chain or branched C10 - C20 alkanol, wherein alkoxylation is carried out using ethylene oxide, propylene oxide, and / or butylene oxide.

15. The fuel composition according to any one of claims 1 to 13, wherein the carrier oil (C) is a polyetheramine obtainable from a 5 - to 30 - fold alkoxylated straight - chain or branched C10 - C20 alkanol, wherein alkoxylation is carried out using ethylene oxide, propylene oxide, and / or butylene oxide, followed by amination.

16. The fuel composition according to any one of the preceding claims, wherein the compound (D) is at least one alkoxylated polyethyleneimine (D1) of the following formula: Formula (IV) or Formula (V) and wherein For X where i = 1 to j, 1 to k, 1 to l, 1 to m, 1 to n, 1 to p, 1 to q, 1 to r or 1 to s i are independently 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-, and most preferably selected from the group consisting of -CH2-CH2-O-, -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-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O- x and y are independently zero or positive integers j, k, l, m, n, p, q, and r are independently zero or positive integers wherein provided that - the sum of x and y in Formula (V) is non - zero - the sum of j, k, l, m, n, p, q, and r is non - zero.

17. The fuel composition according to any one of claims 1 to 15, wherein the compound (D) is at least one alkylphenol - formaldehyde resin having a repeating structural unit of Formula (VI) wherein R 41 is hydrogen or the group –[–X i –]] s –H R 42 is a straight-chain or branched C4 to C 24 alkyl group R 43 is hydrogen or a C1 to C4 alkyl group, X i has the above meanings z is a positive integer from 10 to 80, preferably from 15 to 75, more preferably from 20 to 70, and especially from 25 to 65, and s is a positive integer from 3 to 30, preferably from 5 to 10.

18. The fuel composition according to any one of claims 1 to 15, wherein the compound (D) is at least one alkyl -, aryl -, or alkylaryl sulfonate or sulfate (D3), preferably a sulfonate, more preferably an alkyl sulfonate or an alkylaryl sulfonate, and especially an alkylaryl sulfonate, wherein the alkyl group contains 6 to 24, preferably 8 to 20, more preferably 10 to 18 carbon atoms and may be straight - chain or branched.

19. The fuel composition according to any one of the preceding claims, wherein the compound (F1) is the propoxylated and / or butoxylated reaction product of: (a) one or more fatty acids selected from the group consisting of: lauric acid, myristic acid, palmitic acid, stearic acid, caprylic acid, pelargonic acid, behenic acid, cerotic acid, montanic acid, lignoceric acid, nonadecenoic acid, erucic acid, linoleic acid, erythrocyanic acid, linolenic acid, arachidonic acid, chypanυdoic acid, ricinoleic acid, ceroplastic acid, capric acid, isostearic acid, gadoleic acid, myristoleic acid, palmitoleic acid, linderic acid, oleic acid, umbellic acid, their esters, and their mixtures, and (b) diethanolamine.

20. The fuel composition according to any one of claims 1 to 18, wherein the amide (F2) has Formula (III): R 10 -(C=O)-(NR 11 )-R 12 wherein R 10 is a straight-chain or branched-chain, preferably branched-chain C7 to C 29 alkyl or C7 to C 29 alkenyl, preferably C7 to C 23 alkyl or C7 to C 23 alkenyl R 11 is hydrogen or a C1 to C4 alkyl group, and R 12 is a hydrocarbyl residue containing from 12 to 200 carbon atoms obtainable by the polymerization of olefins.

21. The fuel composition according to claim 20, wherein the carboxylic acid R 10 -COOH is a fatty acid or a fatty acid mixture containing 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms.

22. The fuel composition according to claim 20, wherein the carboxylic acid R 10 -COOH is isononanoic acid.

23. The fuel composition according to any one of claims 1 to 18, wherein the compound (F3) is selected from the group consisting of dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, oleic acid, linoleic acid, trans-linoleic acid, erucic acid, arachidic acid, behenic acid, lignoceric acid, and cerotic acid.

24. The fuel composition according to any one of claims 1 to 18, wherein the compound (F4) is a reaction product of isostearic acid and diethanolamine.

25. The fuel composition according to any one of claims 1 to 18, wherein the compound (F5) is selected from the group consisting of tall oil fatty acids and dimerized tall oil fatty acids.

26. Use of an additive package for improving the properties of a fuel composition for a spark-ignition internal combustion engine, the additive package comprising the following substances according to any one of the preceding claims: - at least one deposit control agent (A), - at least one corrosion inhibitor (B), - at least one carrier oil (C), - at least one cloud point depressant (D), - at least one friction modifier (F) The fuel composition comprises: - 97% to 0% by weight of gasoline and - 3% to 100% by weight of methanol.

27. A method of operating a spark-ignition internal combustion engine using a fuel according to any one of claims 1 to 25.

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