CN116829684A

CN116829684A - Branched primary alkylamines as additives for gasoline fuels

Info

Publication number: CN116829684A
Application number: CN202280011807.8A
Authority: CN
Inventors: J·梅茨杰; M·沃尔特; M·汉斯; S·西奥尼; M·洛曼
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2021-01-27
Filing date: 2022-01-17
Publication date: 2023-09-29
Also published as: EP4284902A1; US20240101919A1; AU2022213776A1; AU2022213776A9; WO2022161803A1

Abstract

The present invention describes the use of specific branched primary alkylamines as additives for gasoline fuels, in particular for reducing fouling of the injector nozzle of direct injection spark ignition engines.

Description

Branched primary alkylamines as additives for gasoline fuels

The present invention describes the use of certain branched amines as additives for gasoline fuels, in particular for reducing fouling of the injector nozzle of direct injection spark ignition engines.

The use of linear amines as additives for different fuels and for different uses has long been known.

EP 450704 discloses a linear C ₁₀ -to C ₂₀ Amine as an additive for reducing fouling of the injectors of diesel engines.

WO 2003/76554 discloses the use of a hydrocarbyl amine having a number average molecular weight of 140 to 255 in the hydrocarbyl moiety as an additive for reducing fouling of the injector nozzle of a direct injection spark ignition engine.

Linear alkylamines are preferred, dodecylamine (laurylamine) being used in the examples.

WO 2004/50806A2 discloses a composition comprising an amine and a Mannich (Mannich) adduct as a detergent for a direct injection spark ignition engine.

Among other amines, tridecylamine is generally disclosed and used for an additive package (additiv package), but no isomer is disclosed.

One disadvantage of linear amines is that they tend to solidify at ambient temperature, so that incorporation of the linear amine into the additive package requires a minimum temperature or heating of the components prior to mixing. In particular laurylamine, as disclosed in WO 2003/76554, is solid at room temperature and therefore needs to be melted before the additive package is formulated. In addition, the additive package containing laurylamine as a component was poor in storage stability at low temperatures (see comparative examples below).

In addition, the linear amine is easily decomposed from the additive package, and thus a larger amount of solvent or stabilizer or compatibilizer is used as an additional component to produce a stable mixture.

The object of the present invention is to develop amines as additives for gasoline fuels which have an activity comparable to or even higher than the linear amines known in the prior art as additives for reducing injector nozzle fouling without showing their disadvantages, but rather are easier to incorporate into additive packages. In addition, the storage stability of the amine-containing additive package should be improved.

This problem is solved by using branched alkylamines as fuel additives for gasoline, said alkyl groups 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.

Another object of the present invention is a gasoline package comprising at least one of these branched alkylamines, at least one deposit control agent and optionally other gasoline additives.

Another object of the invention is a gasoline fuel composition comprising said additive package. The gasoline fuel composition is preferably suitable for use in a spark-ignition engine to reduce injector nozzle fouling in a direct-injection spark-ignition engine.

Accordingly, another object of the present invention is the use of branched primary alkylamines for reducing injector nozzle fouling of direct injection spark ignition engines, said alkyl groups having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms and having at least 1.0, preferably from 1.0 to 8.0, more preferably from 1.5 to 7.0 branches, the use of additive packages comprising said branched primary alkylamines for reducing injector nozzle fouling of direct injection spark ignition engines, and the use of lead-free gasoline compositions comprising a major portion of gasoline suitable for spark ignition engines for reducing injector nozzle fouling of direct injection spark ignition engines.

Branched amines

Branched alkylamines R-NH according to the invention ₂ Is a primary amine bearing an alkyl group R having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms, said alkyl group having at least 1.0, preferably from 1.0 to 8.0, more preferably from 1.5 to 7.0 branches.

In the context of the present invention, "branched" means that the alkyl residue R comprises the desired number of branches. In the case of a single amine with only one branched isomer, the branching of the pure compound can be readily determined according to chemical structure. For mixtures of isomers, the average branching of the mixture is calculated by: the branching of each individual isomer is multiplied by the molar amount of the corresponding isomer in the mixture and then added. Preferably, the branching is determined using the branching coefficient (ISO coefficient) (see below).

The branched primary amine may be used in the form of a mixture of amines having different molecular weights or preferably having one single molecular weight.

Typical examples of such amines are 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, eicosanamine, docosylamine, and mixtures thereof, more preferably nonylamine, tridecylamine, and heptadecylamine, most preferably tridecylamine, and heptadecylamine, and especially tridecylamine.

A preferred example of a branched octylamine is 2-amino-2, 4-trimethyl-pentane.

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

In a preferred embodiment, the branched amines of the invention are obtainable by oligomerization of propylene, isobutylene, 1-butene or 2-butene to form oligomers containing double bonds, followed by hydroformylation and reductive amination with ammonia. The amine produced is typically a mixture of isomers.

In another preferred embodiment, the branched amines of the present invention can be obtained by amination of the corresponding branched alcohols or reductive amination of the corresponding branched aldehydes. In this case, the branching of the amine obtained is identical to that of the base alcohol or aldehyde, since the reaction conditions of the amination or reductive amination generally do not affect the branching of the alkyl group.

In the case of branched tridecylamines, the mixture of isomers may comprise one or more of the following isomers:

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

Most preferred are isomer mixtures with 2,4, 6-hexamethylheptylamine or 2,4, 6-triethylheptylamine as the main component.

Examples of such mixtures of branched amines are tertiary alkyl C obtainable by the Ritter reaction (Ritter reaction) ₁₂ -to C ₁₄ Mixtures of amines (CAS No. 68955-53-3) or C ₁₆ -to C ₂₂ Mixtures of amines.

Amines having tertiary alkyl groups are less preferred because they exhibit toxicity upon inhalation.

Thus, among the branched primary alkylamines of the invention, preference is given to those amines having amine groups bonded to the primary carbon, i.e.having the group-CH ₂ -NH ₂ Is an amine of (2).

Particular preference is given to tridecylamine isomeric mixtures from BASF SE (CAS number 86089-17-0), which are obtained from the corresponding tridecylalcohol isomeric mixtures by amination and have a branching index of 2.2.

The branched alkylamine has a lower melting point than the corresponding linear alkylamine, and therefore, is easier to formulate in an additive package. Such branched alkylamines are often liquid at room temperature, but generally have a lower melting point than the corresponding linear isomer. Having easier formulability means that less solvent is required to achieve a homogeneous formulation than the corresponding linear alkylamine.

It is therefore an object of the present invention to use such branched primary alkyl amines as additives in fuel additive packages to improve the storage stability and/or formulability of gasoline fuel additive packages, said alkyl groups having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms and having at least 1.0, preferably from 1.0 to 8.0, more preferably from 1.5 to 7.0 branches.

Branching coefficient (ISO coefficient)

According to the invention, the degree of branching is preferably described by an ISO coefficient representing the average number of branches of each alkyl group. Thus, for example, at C ₈ In the case of alkyl, the contribution of n-octyl to the ISO factor is 0, the contribution of methylheptyl to the ISO factor is 1, and the contribution of dimethylhexyl to the ISO factor is 2. The lower the ISO coefficient, the more reactive groupsThe greater the linearity of the molecule.

The degree of branching is defined as the number of methyl groups in one molecule of the amine minus 1. The average degree of branching is a statistical average of the degree of branching of the sample molecules. The average degree of branching can preferably be determined by ¹ H-NMR spectroscopy was determined as follows: samples of the amine were first derivatized by 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 at δ=3 to 4 ppm. All methyl, methylene and methine (methene) protons are in the range of 2.4 to 0.4 ppm.<A signal of 1ppm is assigned to methyl. The average degree of branching (ISO coefficient) can be calculated from the spectra obtained in this way as follows:

ISO coefficient= ((a (CH) ₃ )/3)/(A(CH ₂ -NH ₂ )/2))-1

Wherein A (CH) ₃ ) Is the signal area corresponding to the methyl proton, and A (CH ₂ -NH ₂ ) Is CH ₂ -NH ₂ Signal area of methylene protons in the group. Primary amine (H) having methine proton adjacent to amino group ₂ NCHR) can be analyzed similarly. In the case of amines with quaternary carbon atoms adjacent to the amino group, a different and signalable (as-signalling) proton signal can be used to determine the ISO factor.

In the case of branched amines obtained from the corresponding branched alcohols or aldehydes by amination or reductive amination, the ISO coefficients determined according to the above-described method can be used.

Even more preferred ¹ The H-NMR method is carried out without derivatization: alpha-branched primary amine (H) ₂ NCH ₂ The degree of branching (ISO coefficient) of R) is determined by them ¹ And (5) determining an H-NMR spectrum. All NMR spectra were recorded at t= 298.2K on a Bruker Avance III 400 spectrometer for ¹ H, at 400.33MHz, and for ¹³ C, run at 100.66 MHz. The spectrometer is equipped with a 5mm z-gradient broadband viewing intelligent probe. Chemical shifts were referenced to tetramethylsilane (TMS, δ (TMS) =0 ppm). Recording 1H 1D spectra with 64k data points using zg pulse programThe relaxation delay D1 is chosen to be 5 seconds and 64 transients are recorded. For processing in the Bruker TopSpin 4.0.9 software, using 32k data points, an exponential window function (exponential window function) with line broadening of 0.3Hz was applied. The phase correction is performed manually by the user using an automatic baseline correction. Phase sensitive HSQC spectra were recorded using hsqcecetapssp 2.3 pulse sequences with 4k data points in the direct dimension and 256 data points in the indirect dimension, using 8 transients per increment. The experiment is optimized as ¹ J _C-H The coupling constant was 144Hz. The relaxation time delay D1 is set to 1.0 seconds. For processing, the 1024x1024 data points are fourier transformed and a quadratic sine function with a sine bell shift (2) is applied.

Samples were prepared by dissolving the pure analyte in deuterated chloroform with trace TMS as an internal standard. The sample was transferred to a 5mm NMR tube. Deuterated solvents were purchased from Euriso-Top GmbH and used as received.

To determine the ISO coefficient, H is ₂ NCH ₂ R is from delta=2.3-2.95 ppm and is set to a value of 2. The signal from delta=0.6-0.95 ppm aliphatic methyl groups (verified by phase sensitive HSQC spectroscopy) was integrated to give the value I (Me). The degree of branching (ISO coefficient) was calculated according to ISO coefficient=I (Me)/3-1.

Deposit control agent

The gasoline additive package and the corresponding gasoline composition of the present invention each comprise at least one deposit control agent selected from the group consisting of

-a quaternary ammonium compound, which is a compound,

mannich adducts, and

-a polyolefin monoamine or a polyolefin polyamine having a number average molecular weight in the range 300 to 5000, preferably selected from

-quaternary ammonium compounds, and

-a polyolefin monoamine or a polyolefin polyamine having a number average molecular weight in the range of 300 to 5000.

Most preferably the deposit control agent is a polyolefin monoamine or a polyolefin polyamine, in particular a polyisobutene amine having a number average molecular weight in the range 300 to 5000.

The deposit control agent is described in more detail below:

quaternary ammonium compounds

In the context of the present application, at least one quaternary nitrogen component refers to a nitrogen compound quaternized in the presence of or in an acid-free manner, which is preferably obtainable by: a compound comprising at least one oxygen-containing or nitrogen-containing group which reacts with an anhydride and at least one further quaternizable amino group is added to the polycarboxylic anhydride compound and subsequently quaternized.

In most cases, the quaternary nitrogen component is an ammonium compound, however, in the context of the present application the phrase "quaternary nitrogen component" also encompasses morpholinium (morpholinium), piperidinium (piperdinium), piperazinium (piperazinium), pyrrolidinium (pyrrosium), imidazolinium (imidazolinium) or pyridinium (pyridinium) cations.

The quaternary ammonium compound preferably has the formula

⁺ NR ¹ R ² R ³ R ⁴ A ^-

Wherein the method comprises the steps of

A ^- Represents anions, preferably carboxylate radicals R ⁵ COO ^- Or carbonate group R ⁵ O-COO ^- And (2) and

R ¹ 、R ² 、R ³ 、R ⁴ and R is ⁵ Independently of one another, are unsubstituted, linear or branched alkyl, alkenyl or hydroxyalkyl residues having from 1 to 100 carbon atoms, preferably 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 in particular from 1 to 20 carbon atoms,

R ⁵ But also substituted or unsubstituted cycloalkyl or aryl residues having from 5 to 20, preferably from 5 to 12, carbon atoms.

It is also possible that the anions may be multiply negatively charged, for example if anions of dibasic acids are used, in which case the stoichiometric ratio of ammonium ions to anions corresponds to the ratio of positive and negative charges.

The same is true for salts with cations having more than one ammonium ion, such as salts where a substituent connects two or more ammonium ions.

In the organic residue, the carbon atom may be interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, and may be interrupted by C ₆ -C ₁₂ -aryl, C ₅ -C ₁₂ Cycloalkyl or a five-or six-membered oxygen-, nitrogen-and/or sulfur-containing heterocyclic ring, or two of them together form an unsaturated, saturated or aromatic ring, which may be interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, where the radicals mentioned may each be substituted by a functional group, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom and/or heterocyclic ring.

Residue R ¹ To R ⁴ May together form an unsaturated, saturated or aromatic ring, preferably a five-, six-or seven-membered ring (including the nitrogen atom of the ammonium ion).

In this case, the ammonium cation may be a morpholinium, piperidinium, piperazinium, pyrrolidinium, imidazolinium, or pyridinium cation.

In these definitions

C which may be substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and/or heterocycles ₁ -C ₂₀ Alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2, 4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, 1-dimethylpropyl, 1-dimethylbutyl, 1, 3-tetramethylbutyl, benzyl, 1-phenethyl, 2-phenethyl, alpha, alpha-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2, 4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1, 2-di- (methoxycarbonyl) ethyl, 2-methoxycarbonylEthyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1, 3-dioxolane (dioxan) -2-yl, 1, 3-dioxan (dioxan) -2-yl, 2-methyl-1, 3-dioxan-2-yl, 4-methyl-1, 3-dioxan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octoxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl 2, 2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2, 2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl, and

C interrupted by one or more oxygen atoms and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups ₂ -C ₂₀ The alkyl group is, for example, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3, 6-dioxaoctyl, 11-hydroxy-3, 6, 9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4, 8-trioxaundecyl, 15-hydroxy-4, 8, 12-trioxapentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5, 10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3, 6-dioxaoctyl, 11-methoxy-3, 6, 9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4, 8-dioxa-undecyl, 15-methoxy-4, 8, 12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5, 10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxypentyl3, 6-dioxaoctyl, 11-ethoxy-3, 6, 9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4, 8-dioxaundecyl, 15-ethoxy-4, 8, 12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5, 10-oxatetradecyl.

If the two radicals form a ring, they may together be 1, 3-propene, 1, 4-butene, 1, 5-pentene, 2-oxa-1, 3-propene, 1-oxa-1, 3-propene, 2-oxa-1, 3-propene, 1-oxa-1, 3-propenylene (propenylene), 1-aza-1, 3-propenylene, 1-C ₁ -C ₄ -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.

The number of oxygen atoms and/or sulfur atoms and/or imino groups is not limited in any way. Typically, no more than 5, preferably no more than 4, and very particularly preferably no more than 3 will be present in a group.

Furthermore, there is generally at least one carbon atom, preferably at least two carbon atoms, between any two heteroatoms.

The substituted and unsubstituted imino groups can be, for example, imino, methylimino, isopropylimino, n-butylimino, or t-butylimino.

In addition, in the case of the optical fiber,

the functional group may be carboxyl, carboxamide, hydroxyl, di (C) ₁ -C ₄ -alkyl) amino, C ₁ -C ₄ -alkoxycarbonyl, cyano or C ₁ -C ₄ An alkoxy group, which is a group having a hydroxyl group,

c which may be substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and/or heterocycles ₆ -C ₁₂ Aryl is, for example, phenyl, tolyl, xylyl, alpha-naphthyl, beta-naphthyl, 4-diphenyl (diphenyl), 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-nitrophenyl or 4-nitrophenyl, 2, 4-dinitrophenyl or 2, 6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,

c which may be substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and/or heterocycles ₅ -C ₁₂ Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl or saturated or unsaturated bicyclic systems, for example norbornyl (norbornyl) or norbornenyl (norbornenyl),

five-or six-membered oxygen-, nitrogen-and/or sulfur-containing heterocycles are, for example, furyl, thienyl, pyrrolyl, pyridyl, indolyl, benzoxazolyl, dioxolyl (dioxanyl), dioxanyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolinyl, dimethylpyrrolyl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiothienyl, isopropylthienyl or tert-butylthienyl, and

C ₁ To C ₄ Alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

Residue R ¹ To R ⁵ Preferably C ₂ -C ₁₈ -alkyl or C ₆ -C ₁₂ Aryl, more preferably C ₄ -C ₁₆ -alkyl or C ₆ -C ₁₂ Aryl, and even more preferably C ₄ -C ₁₆ -alkyl or C ₆ -aryl.

Residue R ¹ To R ⁵ May be saturated or unsaturated, preferably saturated.

Preferred residue R ¹ To R ⁵ Without carbon removalOr any heteroatom other than hydrogen.

R ¹ To R ⁴ Preferred examples of (C) are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2, 4-trimethylpentyl, 2-propylheptyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, 1-dimethylpropyl, 1-dimethylbutyl, 1, 3-tetramethylbutyl, benzyl, 1-phenethyl, 2-phenethyl, alpha, alpha-dimethylbenzyl, benzhydryl, p-tolylmethyl or 1- (p-butylphenyl) ethyl.

In a preferred embodiment, residue R ¹ To R ⁴ At least one of which is selected from 2-hydroxyethyl, hydroxypropyl-1-yl, hydroxypropyl-2-yl, 2-hydroxybutyl or 2-hydroxy-2-phenethyl.

In one embodiment, R ⁵ Is a polyolefin homopolymer or a polyolefin copolymer, preferably polypropylene, polybutene or polyisobutene residues, having a number average molecular weight (M _n ) 85 to 20000, e.g. 113 to 10000, or 200 to 10000, or 350 to 5000, e.g. 350 to 3000, 500 to 2500, 700 to 2500 or 800 to 1500. Preference is given to polypropylene-, polybutylene-and polyisobutenyl groups, for example of number average molecular weight M _n 3500 to 5000, 350 to 3000, 500 to 2500, 700 to 2500 and 800 to 1500g/mol.

Anion A ^- Preferred examples of (a) are acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, trimethylhexanoic acid, 2-propylheptanoic acid, isononanoic acid, versatic acid, decanoic acid, undecanoic acid, dodecanoic acid, saturated or unsaturated fatty acids having 12 to 24 carbon atoms or mixtures thereof, salicylic acid, oxalic acid mono-C ₁ -C ₄ Alkyl esters, phthalic acid mono-C ₁ -C ₄ Alkyl esters, C ₁₂ -C ₁₀₀ -alkyl succinic acids and C ₁₂ -C ₁₀₀ Anions of alkenyl succinic acids, in particular anions of dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid and polyisobutenyl succinic acid. Other examples are methyl carbonate, ethyl carbonate, n-butyl carbonate, 2-hydroxyethyl carbonate and 2-hydroxypropyl carbonate.

In a preferred embodiment, the quaternized nitrogen compound in the presence of an acid or in an acid-free manner can be obtained by: the addition of a compound comprising at least one oxygen-or nitrogen-containing group which reacts with an anhydride and at least one further quaternizable amino group to a polycarboxylic anhydride compound and subsequent quaternization, in particular quaternization with epoxides (e.g. styrene or propylene oxide) in the absence of free acids, as described in WO 2012/004300, or quaternization with carboxylic esters (e.g. dimethyl oxalate or methyl salicylate). Suitable compounds having at least one oxygen-or nitrogen-containing group which reacts with the anhydride and additionally at least one 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 anhydrides are in particular dicarboxylic acids, such as succinic acid, which have longer-chain hydrocarbon substituents, preferably the number-average molecular weight M of the hydrocarbon substituents _n 200 to 10000, in particular 350 to 5000. Such quaternary ammonium nitrogen compounds are, for example, polyisobutenyl succinic anhydrides (M in which the polyisobutenyl group is M _n Typically 1000) with 3- (dimethylamino) propylamine at 40 c, which constitutes a polyisobutenyl succinic acid monoamide, and which is subsequently quaternized with dimethyl oxalate or methyl salicylate or, in the absence of free acid, with styrene oxide or propylene oxide.

Other quaternized nitrogen compounds suitable for use as compounds are described in

WO 2006/135881 A1, page 5, line 13 to page 12, line 14;

WO 10/132059A 1, page 3, line 28 to page 10, line 25;

WO 2008/060888 A2, page 6, line 15 to page 14, line 29;

WO 2011/095819 A1, page 4, line 5 to page 9, line 29;

GB 2496514A, paragraphs [00012] to [00041 ];

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

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

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

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

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

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

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

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

WO 12/004300, pages 5, lines 20 to 30, page 8, lines 1 to 10, lines 10 and 19, lines 29 to 28, line 3,

each of which is incorporated herein by reference.

In one embodiment, the quaternized ammonium compound has the formula

Wherein in the formula

PIB represents a polyisobutenyl residue, the number average molecular weight M _n 550 to 2300, preferably 650 to 1500, and more preferably 750 to 1300g/mol,

r represents C ₁ -to C ₄ -alkyl or hydroxy-C ₁ -to C ₄ -alkyl, preferably methyl or 2-hydroxypropyl, and

A ^- represents an anion, preferably a carboxylate group R as defined above ⁵ COO ^- Or carbonate group R ⁵ O-COO ^- More preferably an acetate group, a salicylate group or a methyl oxalate group.

In another preferred embodiment, the quaternized ammonium compound has the formula

Wherein in the formula

r represents hydroxy-C ₁ -to C ₄ -alkyl, preferably 2-hydroxypropyl.

In another embodiment, the quaternized compound has the formula

Wherein in the formula

r represents C ₁ -to C ₄ -alkyl or hydroxy-C ₁ -to C ₄ -alkyl, preferably methyl, and

A ^- represents an anion, preferably a carboxylate group R as defined above ⁵ COO ^- Or carbonate group R ⁵ O-COO ^- More preferably a salicylate group or methyl oxalate group.

In another embodiment, the quaternized ammonium compound has the formula

Wherein in the formula

R ^a Represents C ₁ -C ₂₀ -alkyl, preferably C ₉ -to C ₁₇ Alkyl, more preferably undecyl, tridecyl, pentadecyl or heptadecyl,

R ^b represents hydroxy-C ₁ -to C ₄ -alkyl, preferably 2-hydroxypropyl or 2-hydroxybutyl, and

A ^- represents an anion, preferably a carboxylate group R as defined above ⁵ COO ^- More preferably R ⁵ COO ^- Carboxylic acid ester groups of fatty acids, especially A ^- Monoesters which are acetate, 2-ethylhexanoate, oleate, polyisobutenyl succinate or polyisobutenyl succinate.

In one embodiment, the quaternized ammonium compound has the formula

Wherein in the formula

i=1 to n and X of 1 to m _i Independently of one another selected from-CH ₂ -CH ₂ -O-、-CH ₂ -CH(CH ₃ )-O-、-CH(CH ₃ )-CH ₂ -O-、-CH ₂ -C(CH ₃ ) ₂ -O-、-C(CH ₃ ) ₂ -CH ₂ -O-、-CH ₂ -CH(C ₂ H ₅ )-O-、-CH(C ₂ H ₅ )-CH ₂ -O-and-CH (CH) ₃ )-CH(CH ₃ ) -O-, preferably selected from-CH ₂ -CH(CH ₃ )-O-、-CH(CH ₃ )-CH ₂ -O-、-CH ₂ -C(CH ₃ ) ₂ -O-、-C(CH ₃ ) ₂ -CH ₂ -O-、-CH ₂ -CH(C ₂ H ₅ )-O-、-CH(C ₂ H ₅ )-CH ₂ -O-and-CH (CH) ₃ )-CH(CH ₃ ) O-more preferably selected from-CH ₂ -CH(CH ₃ )-O-、-CH(CH ₃ )-CH ₂ -O-、-CH ₂ -C(CH ₃ ) ₂ -O-、-C(CH ₃ ) ₂ -CH ₂ -O-、-CH ₂ -CH(C ₂ H ₅ ) -O-and-CH (C) ₂ H ₅ )-CH ₂ O-is most preferably selected from-CH ₂ -CH(C ₂ H ₅ )-O-、-CH(C ₂ H ₅ )-CH ₂ -O-、-CH ₂ -CH(CH ₃ ) -O-and-CH (CH) ₃ )-CH ₂ -O-, and in particular selected from-CH ₂ -CH(CH ₃ ) -O-and-CH (CH) ₃ )-CH ₂ -O-，

m and n are each independently of the other 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 in particular from 15 to 25,

r represents C ₁ -to C ₄ -alkyl, preferably methyl, and

In another preferred embodiment, the quaternized ammonium compound is of the formula

Wherein in the formula

R ^a And R is ^b Independently of one another, represent C ₁ -C ₂₀ -alkyl or hydroxy-C ₁ -to C ₄ -alkyl, preferably R ^a Represents C ₁ -C ₂₀ -alkyl, preferably ethyl, n-butyl, n-octyl, n-dodecyl, tetradecyl or hexadecyl, and R ^b Represents hydroxy-C ₁ -to C ₄ Alkyl groups, preferably 2-hydroxypropyl groups,

A ^- represents an anion, preferably a carboxylate group R as defined above ⁵ COO ^- Or carbonate group R ⁵ O-COO ^- More preferably C ₁₂ -C ₁₀₀ -alkyl succinic acids and C ₁₂ -C ₁₀₀ Alkenyl succinic acids, in particular dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid and polyisobutenyl succinic acid.

Mannich adducts

Typical mannich adducts are described in US 8449630 B2, preferably mannich adducts of formula I in US 8449630 B2, which are incorporated herein by reference.

In a preferred embodiment, the mannich adducts are obtainable as described in US 8449630 B2, column 7, line 35 to column 9, line 52.

Preferably the mannich adducts may be obtained by reacting:

-at least one hydrocarbyl-substituted phenol, preferably a phenol of formula V in US 8449630 B2, more preferably para-hydrocarbyl-substituted phenol or para-hydrocarbyl-substituted o-cresol, and-at least one aldehyde, preferably acetaldehyde or formaldehyde, more preferably formaldehyde, and-at least one amine of variant 2 in US 8449630 B2, preferably selected from the group consisting of octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosamine, cyclooctamine, cyclodecylamine, di-N-butylamine, diisobutylamine, di-t-butylamine, dipentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, dinonylamine, didecylamine, N-methylcyclohexylamine, dicyclohexylamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrabutylenepentamine, N-pentabutylenetetramine, N-dipropylmethylenediamine, N-dipropyleneethylene-1, 2-diamine, N-dimethylpropylene1, 3-diamine, N-diethylpropylidene-1, 3-diamine, N-dipropylpropylene1, 3-diamine, N, N-diethylbutylene-1, 4-diamine, N-dipropylbutylene-1, 4-diamine, N-dimethylpentylene-1, 3-diamine, N-diethylpentylene-1, 5-diamine, N, n-dipropylenepentylene-1, 5-diamine, N-dimethylhexylene-1, 6-diamine, N-diethylhexylene-1, 6-diamine, N-dipropylene1, 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, N-dimethylamino) butyl ] amine, bis [4- (N, N-diethylamino) 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) propyl ] amine, bis [4- (N, N-dimethylamino) butyl ] amine, bis [4- (N, N-diethylamino) butyl ] amine, bis [4- (N, N-dimethylamino) butyl ] amine, bis [5- (N, N-dimethylamino) pentyl ] amine, bis [6- (N, N-diethylamino) propyl ] amine, bis [ N, N-diethylamino ] propyl ] amine, bis [2- (N, N-dimethylamino) propyl ] amine Tris [3- (N, N-dimethylamino) propyl ] amine, tris [3- (N, N-diethylamino) 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, N-dipropylamino) butyl ] amine, tris [5- (N, N-dimethylamino) pentyl ] amine, tris [5- (N, N-diethylamino) pentyl ] amine, tris [5- (N, N-dipropylamino) pentyl ] amine, tris [6- (N, N-dimethylamino) hexyl ] amine, tris [6- (N, N-diethylamino) -hexyl ] amine and tris [6- (N, N-dipropylamino) hexyl ] amine,

More preferably selected from dimethylamine, diethylamine, di-N-butylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-dimethylpropylene1, 3-diamine and N, N-diethylpropylidene-1, 3-diamine.

The number average molecular weight Mn of the hydrocarbyl residue of the at least one hydrocarbyl-substituted phenol is preferably from 85 to 5000, preferably from 113 to 2500, more preferably from 550 to 1500, and in particular from 750 to 1100.

In a preferred embodiment, the hydrocarbyl residue is a polyisobutene group having the molecular weight described above, more preferably derived from a "reactive" polyisobutene group as defined in US 8449630 B2.

In a preferred embodiment, the Mannich adducts have the formula

Or the following

Wherein the method comprises the steps of

R ¹⁰ Is a hydrocarbyl residue, whichA 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 polyisobutene groups having the abovementioned molecular weights, more preferably derived from "reactive" polyisobutene groups,

R ¹¹ is hydrogen, methyl, ethyl, isopropyl, n-butyl, t-butyl, but-2-yl or pentyl, preferably hydrogen or methyl, and more preferably methyl,

R ¹² and R is ¹³ Independently of one another C ₁ -to C ₆ -alkyl, preferably C ₁ -to C ₄ -alkyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, even more preferably methyl, ethyl or n-butyl, or R ¹² And R is ¹³ Together with the nitrogen atom form a five-or six-membered ring, preferably a pyrrolidine, piperidine or morpholine ring, and

R ¹⁴ 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.

Polyolefin monoamines or polyamines

The polyolefin monoamines or polyolefin polyamines are preferably based on polypropylene or on highly reactive (i.e. having predominantly terminal double bonds) or conventional (i.e. having predominantly internal double bonds) polybutenes or in particular M _n Polyisobutene of=300 to 5000, more preferably 500 to 2500 and especially 700 to 2500. Such additives, based on highly reactive polyisobutenes, which can be prepared from polyisobutenes which can contain up to 20% by weight of n-butene units, are prepared by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known, inter alia, from EP-A244 616. When polybutenes or polyisobutenes having predominantly internal double bonds (generally in the β and γ positions) are used as starting materials in the preparation of additives, the possible preparation routes are: by chlorination and subsequent amination, or by use of air or air Ozone oxidizes double bonds to give carbonyl compounds or carboxyl compounds, and then aminates under reducing (hydrogenation) conditions. The amine used herein for amination may be, for example, ammonia, monoamines or the polyamines described above. Corresponding additives based on polypropylene are described more particularly in WO-A94/24231.

Other specific additives comprising monoamino groups are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization p=5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as more particularly described in WO-a 97/03946.

Other specific additives containing monoamino groups are compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of amino alcohols, as described more particularly in DE-A196 20 262.

An example of a particularly useful polyalkylene group is a polyisobutenyl group, which is derived from a so-called "highly reactive" polyisobutene characterized by a high content of terminal double bonds. The terminal double bond being an alpha-olefinic double bond of the type

Which are also collectively referred to as vinylidene double bonds. Suitable highly reactive polyisobutenes are, for example, polyisobutenes having a proportion of vinylidene double bonds of greater than 70 mol%, in particular greater than 80 mol% or greater than 85 mol%. Polyisobutenes having a homogeneous polymer backbone are particularly preferred. In particular those polyisobutenes formed from isobutene units to the extent of at least 85% by weight, preferably to the extent of at least 90% by weight and more preferably to the extent of at least 95% by weight, have a homogeneous polymer skeleton. The number average molecular weight of the highly reactive polyisobutene is preferably within the above-mentioned range. Furthermore, the polydispersity of the highly reactive polyisobutene may be in the range from 1.05 to 7, in particular from about 1.1 to 2.5, for example less than 1.9 or less than 1.5. Polydispersity is understood to mean the quotient of the weight average molecular weight Mw divided by the number average molecular weight Mn.

Particularly suitable highly reactive polyisobutenes are, for example, those from BASF SEGlissopal brand, in particular1000(Mn＝1000)、/>V33 (mn=550) and +.>2300 (mn=2300) and mixtures thereof. Other number average molecular weights can be established in a manner known in principle by mixing polyisobutenes having different number average molecular weights or by extractive enrichment of polyisobutenes having a particular molecular weight range.

Since these polyisobutenes have a high proportion of vinylidene double bonds, they are particularly reactive for carrying out the hydroformylation reaction and subsequent amination, preferably with ammonia, to give the corresponding polyisobutene amines, which represents a preferred embodiment of the present invention.

Corrosion inhibitors

In principle, all compounds known in the art for fuel applications can be used as corrosion inhibitors.

Suitable corrosion inhibitors are, for example, succinates or half esters (especially with polyols), fatty acid derivatives (e.g. oleates), oligomeric fatty acids (e.g. dimerised fatty acids), substituted ethanolamines and products sold under the trade names RC 4801 (Rhein Chemie Mannheim, germany) or HiTEC 536 (Afton Corporation).

According to US 6043199, the latter is believed to be the reaction product of a linear or branched alkyl or alkenyl substituted succinic anhydride with a substituted amino imidazoline, resulting in a succinimide or amine substituted succinimide, which is believed to be linear or branched alkyl or alkenyl substituted.

In a preferred embodiment, the corrosion inhibitor is selected from

Fatty acids or fatty acid derivatives, preferably oleic acid or its esters,

oligomeric fatty acids, preferably dimeric fatty acids, more preferably dimeric oleic acid (CAS: 61788-89-4),

-alkyl-or alkenyl-substituted succinic acids, esters or half-esters thereof, and

olefin-carboxylic acid copolymers (see below).

In a more preferred embodiment, the corrosion inhibitor is selected from

olefin-carboxylic acid copolymers (see below).

Alkyl-or alkenyl-substituted succinic acids, esters or half-esters thereof

Succinic acid, its esters or half-esters are preferably substituted by C ₈ -to C ₁₀₀ -alkyl or C ₈ -to C ₁₀₀ -alkenyl substitution.

In a preferred embodiment, the succinic acid or half-ester thereof corresponds to the formula

/>

Wherein the method comprises the steps of

R ²⁰ Is C ₈ -to C ₁₀₀ -alkyl or C ₈ -to C ₁₀₀ -alkenyl, preferably C ₈ -to C ₁₀₀ -alkenyl groups, more preferably C ₁₂ -to C ₉₀ -alkenyl groups, and even more preferably C ₁₆ -to C ₈₀ -alkenyl groups, and

R ²¹ is hydrogen or C ₁ -to C ₂₀ -alkyl or C ₂ -to C ₄ Hydroxyalkyl, preferably hydrogen.

Basic succinic anhydride can be obtained by C ₈ -to C ₁₀₀ Thermal olefination (thermal ene reaction) of olefins, preferably oligomers or polymers of propylene, 1-butene or isobutene, with maleic anhydride. The above corrosion inhibitors may be obtained from the anhydride by hydrolysis or reaction with a suitable alcohol.

Olefin-carboxylic acid copolymers

The olefin-carboxylic acid copolymer (a) is a copolymer obtainable by:

-copolymerizing in a first reaction step (I) the following components

(Aa) at least one ethylenically unsaturated mono-or dicarboxylic acid or derivative thereof, preferably a dicarboxylic acid,

(Ab) at least one alpha-olefin having at least 12 up to 30 carbon atoms and comprising 30 carbon atoms,

(Ac) optionally at least one other aliphatic or cycloaliphatic olefin having at least 4 carbon atoms and being different from (Ab), and

(Ad) optionally one or more further copolymerizable monomers other than the monomers (Aa), (Ab) and (Ac), selected from

(Ada) a vinyl ester,

(Adb) a vinyl ether and (iii) a vinyl ether,

(Adc) a (meth) acrylate of an alcohol having at least 5 carbon atoms,

(Add) allyl alcohol or an ether thereof,

(Ade) N-vinyl compounds selected from the group consisting of heterocyclic vinyl compounds containing at least one nitrogen atom, N-vinylamides or N-vinyllactams,

(Adf) an ethylenically unsaturated aromatic compound,

(Adg) alpha, beta-ethylenically unsaturated nitriles,

(Adh) (meth) acrylamide, and

(Adi) an allylamine, which is a salt of a vinyl alcohol,

then

In a second optional reaction step (II), the anhydride or carboxylate functions present in the copolymer obtained from (I) are partially or fully hydrolyzed and/or saponified, wherein the second reaction step is performed at least when the copolymer obtained from reaction step (I) does not contain any free carboxyl functions.

Description of copolymer (A)

The monomer (Aa) is at least one, preferably one to three, more preferably one or two and most preferably exactly one ethylenically unsaturated, preferably α, β -ethylenically unsaturated, mono-or dicarboxylic acid or derivative thereof, preferably a dicarboxylic acid or derivative thereof.

Derivatives are understood to mean

The corresponding anhydride in monomeric or polymeric form,

mono-or dialkyl esters, preferably mono-C ₁ -C ₄ -alkyl esters or di-C ₁ -C ₄ Alkyl esters, more preferably monomethyl or dimethyl esters, or the corresponding monoethyl or diethyl esters, and

mixed esters, preferably with different C' s ₁ -C ₄ Mixed esters of alkyl components, more preferably mixed methylethyl esters.

Preferably, the derivative is an anhydride or di-C in monomeric form ₁ -C ₄ Alkyl esters, more preferably anhydrides in monomeric form.

In the context of the present application, C ₁ -C ₄ Alkyl is understood to mean methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl and ethyl, more preferably methyl.

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

Examples of non- α, β -ethylenically unsaturated mono-or dicarboxylic acids 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.

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 herein as (meth) acrylic acid), and more preferably acrylic acid.

Particularly preferred derivatives of alpha, beta-ethylenically unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate.

Examples of dicarboxylic acids are maleic acid, fumaric acid, itaconic acid (2-itaconic acid), citraconic acid (2-methyl maleic acid), glutaconic acid (pent-2-ene-1, 5-dicarboxylic acid), 2, 3-dimethyl maleic acid, 2-methyl fumaric acid, 2, 3-dimethyl fumaric acid, methylene malonic acid and tetrahydrophthalic acid, preferably maleic acid and fumaric acid, and more preferably maleic acid, and derivatives thereof.

More particularly, the monomer (Aa) is maleic anhydride.

The monomer (Ab) is at least one, preferably one to four, more preferably one to three, even more preferably one or two and most preferably exactly one a-olefin having at least 12 up to 30 carbon atoms and comprising 30 carbon atoms. The alpha-olefin (Ab) preferably has at least 14, more preferably at least 16 and most preferably at least 18 carbon atoms. Preferably, the α -olefin (Ab) has up to 28 carbon atoms and comprises 28 carbon atoms, more preferably up to 26 carbon atoms and comprises 26 and most preferably up to 24 carbon atoms and comprises 24 carbon atoms.

Preferably, the alpha-olefin may be one or more linear or branched 1-olefins, preferably linear 1-olefins.

Examples thereof 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.

Other examples of alpha-olefins (Ab) are those of C ₂ To C ₁₂ Olefins, preferably C ₃ To C ₁₀ Olefins, more preferably C ₄ To C ₆ An olefin of an oligomer or polymer of 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.

Specific examples of alpha-olefins (Ab) include oligomers and polymers of propylene, 1-butene, 2-butene, isobutylene and mixtures thereof, particularly oligomers and polymers of propylene or isobutylene, or oligomers and polymers of mixtures of 1-butene and 2-butene. Among the oligomers, trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.

In addition to the olefin (Ab), at least one, preferably one to four, more preferably one to three, even more preferably one or two and especially exactly one other aliphatic or cycloaliphatic olefin (Ac) having at least 4 carbon atoms and being different from (Ab) may optionally be incorporated into the copolymers of the invention by polymerization.

The olefin (Ac) may be an olefin having a terminal (alpha-) double bond, or an olefin having a non-terminal double bond, preferably an alpha-double bond. The olefin (Ac) preferably comprises an olefin having from 4 to less than 12 or more than 30 carbon atoms. If the olefin (Ac) is an olefin having 12 to 30 carbon atoms, the olefin (Ac) does not have an alpha-double bond.

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

Examples of cycloaliphatic olefins (Ac) are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, alpha-pinene or beta-pinene and mixtures thereof, limonene (limonene) and norbornene.

Other examples of olefins (Ac) are polymers having more than 30 carbon atoms of: propylene, 1-butene, 2-butene or isobutene, or an olefin mixture comprising the latter, preferably isobutene, or an olefin mixture comprising the latter, more preferably an average molecular weight M _w In the range of 500 to 5000g/mol, preferably 650 to 3000g/mol and more preferably 800 to 1500g/mol.

Preferably, the oligomer or polymer comprising isobutylene in copolymerized form has a high content of terminal olefinic double bonds (alpha-double bonds), for example at least 50 mole%, preferably at least 60 mole%, more preferably at least 70 mole%, and most preferably at least 80 mole%.

For the preparation of said oligomers or polymers comprising isobutene in copolymerized form, suitable isobutene sources are pure isobutene or isobutene-containing C4 hydrocarbon streams, such as C4 raffinates (in particular "raffinate 1"), C4 cuts (cuts) from isobutane dehydrogenation, C4 cuts from steam crackers and from FCC crackers (fluid catalytic cracking), with the proviso that they are substantially free of 1, 3-butadiene present therein. The C4 hydrocarbon stream from the FCC refinery unit is also referred to as the "b/b" stream. Other suitable isobutylene-containing C4 hydrocarbon streams are, for example, propylene-isobutane co-oxidized product streams or product streams from metathesis units, which are typically employed after conventional purification and/or concentration. Suitable C4 hydrocarbon streams typically contain less than 500ppm, preferably less than 200ppm butadiene. The presence of 1-butene and the presence of cis-2-butene and trans-2-butene are not substantially critical. Typically, the concentration of isobutene in the C4 hydrocarbon stream is in the range of 40 to 60 wt.%. For example, raffinate 1 typically consists essentially of 30 wt.% to 50 wt.% isobutene, 10 wt.% to 50 wt.% 1-butene, 10 wt.% to 40 wt.% cis-2-butene and trans-2-butene, and 2 wt.% to 35 wt.% butane; in this polymerization process, the unbranched butenes in raffinate 1 are generally almost inert and only isobutene is polymerized.

In a preferred embodiment, the monomer source for the polymerization is an technical grade C4 hydrocarbon stream, in particular a raffinate 1 stream, a b/b stream from an FCC refinery unit, a product stream from propylene-isobutane co-oxidation or a product stream from a metathesis unit, having an isobutene content of from 1 to 100 wt%, in particular from 1 to 99 wt%, in particular from 1 to 90 wt%, more preferably from 30 to 60 wt%.

Particularly when raffinate 1 streams are used as the isobutene source, it has been found useful to use water as the sole initiator or as other initiator, particularly when the polymerization is carried out at temperatures of from-20 ℃ to +30 ℃, particularly from 0 ℃ to +20 ℃. However, at temperatures of-20 ℃ to +30 ℃, particularly at temperatures of 0 ℃ to +20 ℃, when using a raffinate 1 stream as the isobutene source, no initiator may be used.

The isobutylene-containing monomer mixture may contain small amounts of contaminants, such as water, carboxylic acids, or mineral acids, without any critical yield or selectivity loss. It is desirable to avoid the accumulation of such impurities by removing such deleterious substances from the isobutylene-containing monomer mixture, for example by adsorption onto solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

Although less preferred, it is also possible to convert isobutene or a hydrocarbon mixture containing isobutene with a monomer mixture of ethylenically unsaturated monomers copolymerizable with isobutene. If isobutene is copolymerized with a monomer mixture of suitable comonomers, the monomer mixture comprises preferably at least 5% by weight, more preferably at least 10% by weight and in particular at least 20% by weight of isobutene, and preferably up to 95% by weight, more preferably up to 90% by weight and in particular up to 80% by weight of comonomers.

In a preferred embodiment, the mixture of olefins (Ab) and optionally (Ac), on average to their molar amount, has at least 12 carbon atoms, preferably at least 14, more preferably at least 16 and most preferably at least 17 carbon atoms.

For example, the average value of carbon atoms of a 2:3 mixture of docosene and tetradecene is 0.4×22+0.6× 14=17.2.

The upper limit is less relevant and generally does not exceed 60 carbon atoms, preferably does not exceed 55, more preferably does not exceed 50, even more preferably does not exceed 45 and in particular does not exceed 40 carbon atoms.

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

(Ada) a vinyl ester,

(Adb) a vinyl ether and (iii) a vinyl ether,

(Adc) a (meth) acrylate of an alcohol having at least 5 carbon atoms,

(Add) allyl alcohol or an ether thereof,

(Adf) an ethylenically unsaturated aromatic compound, and

(Adg) alpha, beta-ethylenically unsaturated nitriles,

(Adh) (meth) acrylamide, and

(Adi) allylamine.

Examples of vinyl esters (Ada) are C ₂ -to C ₁₂ Vinyl esters of carboxylic acids, preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl caproate, vinyl caprylate, vinyl 2-ethylhexanoate, vinyl caprate and vinyl versatate 5 to 10, preferably the following acids: 2, 2-dimethylpropionic acid (pivalic acid, versatic acid 5), 2-dimethylbutyric acid (neohexanoic acid, versatic acid 6), 2-dimethylpentanoic acid (neoheptanoic acid, versatic acid 7), 2-dimethylhexanoic acid (neooctanoic acid, versatic acid 8), 2-dimethylheptanoic acid (neononanoic acid, versatic acid 9) or 2, 2-dimethyloctanoic acid (neodecanoic acid, versatic acid 10).

Examples of vinyl ethers (Adb) are C ₁ -to C ₁₂ Vinyl ethers of alkanols, preferably vinyl ethers of the following alcohols: 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.

Preferred (meth) acrylates (Adc) are C ₅ -to C ₁₂ -the (meth) acrylic acid esters of alkanols, preferably the (meth) acrylic acid esters of the following alcohols: n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol or 2-propylheptanol. Particularly preferred are amyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate.

Examples of monomers (Add) are C ₂ -to C ₁₂ Allyl alcohol and allyl ether of alkanols, preferably allyl ether of the following alcohols: 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.

Examples of heterocyclic vinyl compounds (Ade) containing at least one nitrogen atom are N-vinylpyridine, N-vinylimidazole and N-vinylmorpholine.

Preferred compounds (Ade) are N-vinylamides or N-vinyllactams.

Examples of N-vinylamides or N-vinyllactams (Ade) are N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and N-vinylcaprolactam.

Examples of ethylenically unsaturated aromatic compounds (Adf) are styrene and alpha-methylstyrene.

Examples of α, β -ethylenically unsaturated nitriles (Adg) are acrylonitrile and methacrylonitrile.

Examples of (meth) acrylamides (Adh) are acrylamide and methacrylamide.

Examples of allylamine (Adi) are allylamine, dialkylallylamine and trialkylallylammonium halides.

Preferred monomers (Ad) are (Ada), (Adb), (Adc), (Ade) and/or (Adf), more preferably (Ada), (Adc) and/or (Adc), even more preferably (Ada) and/or (Adc), and in particular (Adc).

The incorporation ratio of the monomers (Aa) and (Ab) and optionally (Ac) and optionally (Ad) in the polymer obtained from reaction step (I) is generally as follows:

the molar ratio of (Aa)/((Ab) and (Ac)) (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, in particular from 2:1 to 1:2, and in particular from 1.5:1 to 1:1.5. In the preferred particular case of maleic anhydride as monomer (Aa), the molar incorporation ratio of maleic anhydride to monomers ((Ab) and (Ac)) (in total) is about 1:1.

The molar ratio of monomer (Ab) to monomer (Ac), 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 in particular from 1:0.5 to 1.5.

In a preferred embodiment, no optional monomer (Ac) is present other than monomer (Ab).

The proportion of the one or more monomers (Ad), if present, is generally from 5 to 200 mol%, preferably from 10 to 150 mol%, more preferably from 15 to 100 mol%, even more preferably from 20 to 50 mol%, and in particular from 0 to 25 mol%, based on the amount of monomers (Aa), (Ab) and optionally (Ac) (total).

In a preferred embodiment, no optional monomer (Ad) is present.

In the second reaction step (II), the anhydride or carboxylate functions present in the copolymer obtained from (I) are partially or fully hydrolyzed and/or saponified.

If the copolymer obtained from reaction step (I) does not contain free carboxylic acid groups, reaction step (II) is necessary.

Hydrolysis of the anhydride groups is preferred over saponification of the ester groups.

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

For hydrolysis, an amount of water corresponding to the desired level of hydrolysis is added based on the anhydride functionality present, and the copolymer obtained from (I) is heated in the presence of the added water. In general, the temperature is preferably from 20 to 150℃sufficient for the purpose, preferably from 60 to 100 ℃. If desired, the reaction may be carried out under pressure to prevent escape of water. Under these reaction conditions, typically, the anhydride functionality in the copolymer is selectively converted, while any carboxylate functionality present in the copolymer reacts, at least to a small extent.

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

The strong base used may preferably be an alkali or alkaline earth metal hydroxide, oxide, carbonate or bicarbonate.

Then, the copolymer obtained from (I) is heated in the presence of added water and strong base. In general, the temperature is preferably from 20 to 130℃sufficient for the purpose, preferably from 50 to 110 ℃. The reaction may be carried out under pressure, if desired.

The carboxylate functionality may also be hydrolyzed with water in the presence of an acid. The acid used is preferably an inorganic acid, carboxylic acid, sulphonic acid or phosphoric acid having a pKa of not more than 5, more preferably not more than 4.

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

In a preferred embodiment in which the anhydride, in particular maleic anhydride, is the monomer (Aa), the anhydride moiety is partially or fully hydrolyzed, in particular fully hydrolyzed, while the ester groups potentially present in the copolymer remain intact. In this case, the saponification in step (II) does not occur.

The copolymer obtained from (I) is then heated in the presence of added water and acid. In general, the temperature is preferably from 40 to 200℃sufficient for the purpose, preferably from 80 to 150 ℃. The reaction may be carried out under pressure, if desired.

If the copolymer obtained from step (II) still comprises residues of acid anions, these 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 halides or contain sulfur or nitrogen.

The weight average molecular weight Mw of the copolymer obtained from reaction step (II) is generally from 0.5 to 20kDa, preferably from 0.6 to 15, more preferably from 0.7 to 7, even more preferably from 1 to 7, and in particular from 1.5 to 4kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standards).

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

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 in particular from 1.5 to 3.

The content of acid groups in the copolymer is preferably 1 to 8mmol/g copolymer, more preferably 2 to 7.5, even more preferably 3 to 7mmol/g copolymer.

In a preferred embodiment, the copolymer contains a high proportion of adjacent carboxylic acid groups, as determined by measurement of adjacency (adjacency). For this purpose, a sample of the copolymer was heat treated between two teflon films at a temperature of 290 ℃ for 30 minutes and FTIR spectra were recorded at the bubble free position. The IR spectrum of teflon was subtracted from the obtained spectrum, the layer thickness was determined and the content of cyclic anhydride was determined.

In a preferred embodiment, the adjacency is at least 10%, preferably at least 15%, more preferably at least 20%, even more preferably at least 25%, and in particular at least 30%.

The olefin-carboxylic acid copolymer (a) is applied in the form of a free acid (i.e. the presence of COOH groups), or in the form of an anhydride, which may be an intramolecular anhydride or an intermolecular anhydride linking two dicarboxylic acid molecules together, preferably in the form of a free acid. To a small extent, some of the carboxylic acid functionality may be present in salt form, for example in the form of a base or alkali metal salt, or in the form of an ammonium or substituted ammonium salt, depending on the pH of the liquid phase. Preferably at least 50% of all carboxylic acid groups can be used as COOH-groups in the form of free acids, more preferably at least 66%, very preferably at least 75%, even more preferably at least 85%, and in particular at least 95%. A single olefin-carboxylic acid copolymer (a) or a mixture of different olefin-carboxylic acid copolymers (a) may be used.

Carrier oil

The carrier oils used in addition may be of mineral or synthetic nature. Suitable mineral carrier oils are fractions obtained in crude oil processing, for example bright stock or base oils having a viscosity, for example from SN 500-2000 grades; and aromatic hydrocarbons, paraffinic hydrocarbons, and alkoxyalkanols. Also useful are fractions obtained in mineral oil refining and referred to as "hydrocracked oils" (vacuum distilled fractions boiling in the range of about 360 ℃ to 500 ℃ which can be obtained from natural mineral oils that have been catalytically hydrogenated and isomerized and dewaxed under high pressure). Also suitable are mixtures of the above-mentioned mineral carrier oils.

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

Examples of suitable polyolefins are M _n Olefin polymers of=400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or unhydrogenated).

Examples of suitable polyethers or polyetheramines are preferably those comprising polyoxy-C ₂ -to C ₄ -a compound of alkylene moieties obtainable by the following process: make C ₂ -to C ₆₀ -alkanols, C ₆ -to C ₃₀ -alkanediol, mono-C ₂ -to C ₃₀ -alkylamines or di-C ₂ -to C ₃₀ -alkylamines, C ₁ -to C ₃₀ -alkylcyclohexanols or C ₁ -to C ₃₀ The alkylphenols are reacted with 1 to 30mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or per amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described more particularly in EP-A310 875, EP-A356 725, EP-A700 985 and U.S. Pat. No. 4,877,416. For example, the polyetheramine used may be poly-C ₂ -to C ₆ -alkylene oxide amines or functional derivatives thereof. Typical examples thereof are tridecyl alcohol butoxylate or isotridecyl alcohol butoxylate, isononyl phenol butoxylate and polyisobutenyl alcohol butoxylate and propoxylate, and the corresponding reaction products with ammonia.

Examples of carboxylic acid esters of long-chain alkanols are more particularly esters of monocarboxylic, dicarboxylic or tricarboxylic acids with long-chain alkanols or polyols, as described more particularly in DE-A38 38 918. The monocarboxylic, dicarboxylic or tricarboxylic acids used may be aliphatic or aromatic acids; particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, from 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 (trimellitates) of isooctanol, isononanol, isodecanol and isotridecyl alcohol, for example di (n-tridecyl) phthalate or di (isotridecyl) phthalate.

Other suitable carrier oil systems are described, for example, in DE-A38 26 608, DE-A41 42 241, DE-A43 09 074, EP-A452 328 and EP-A548 617.

Examples of particularly suitable synthetic carrier oils are alcohol-initiated polyethers having from about 5 to 35, preferably from about 5 to 30, more preferably from 10 to 30 and in particular from 15 to 30C per alcohol molecule ₃ -to C ₆ Alkylene oxide units, such as propylene oxide, n-butylene oxide and isobutane oxide units, or mixtures thereof. Non-limiting examples of suitable starter alcohols are long-chain alkanols or phenols substituted by long-chain alkyl groups, in particular straight-chain or branched C ₆ -to C ₁₈ -an alkyl group. Specific examples include tridecyl alcohol, heptadecyl alcohol, and nonylphenol. Particularly preferred alcohol-initiated polyethers are monoaliphatic C ₆ -to C ₁₈ -alcohol and C ₃ -to C ₆ Reaction products of alkylene oxides (polyether products). Monobasic aliphatic C ₆ -C ₁₈ Examples of alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol and structural and positional isomers thereof. The alcohols may be used in the form of pure isomers or as technical grade mixtures. A particularly preferred alcohol is tridecyl alcohol. C (C) ₃ -to C ₆ Examples of alkylene oxides are propylene oxide (e.g. 1, 2-propylene oxide), butylene oxide (e.g. 1, 2-butylene oxide, 2, 3-butylene oxide), isobutylene or tetrahydrofuran, pentane oxide and hexane oxide. Of these, C is particularly preferred ₃ -to C ₄ Alkylene oxides, i.e. propylene oxide (e.g. 1, 2-propylene oxide) and butylene oxide (e.g. 1, 2-butylene oxide, 2, 3-butylene oxide) and isobutylene oxide. In particular, butylene oxide is used.

Other suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A10 102 913.

Particular carrier oils are synthetic carrier oils, with particular preference being given to the alcohol-initiated polyethers described above.

Other additives

Typical other additives in the additive package or fuel of the present invention may be friction modifiers, dehazers (dehazers), antioxidants, metal deactivators and solvents for the package.

Friction modifier

Suitable friction modifiers are generally based on fatty acids or fatty acid esters. Typical examples are tall oil (tall oil) fatty acids, as described for example in WO 98/004656, and glycerol monooleate. The reaction products of natural or synthetic oils (e.g. triglycerides) with alkanolamines described in US 6743266 B2 are also suitable as such friction modifiers.

Preferred lubricity improvers are described in WO 15/059063 and WO 10/005720. Furthermore, hydroxy-substituted tertiary amines as disclosed in WO 2014/23853 are preferred as friction modifiers.

Demisting agent

Suitable defogging agents are, for example, alkali metal salts or alkaline earth metal salts of alkyl-substituted phenol sulfonates and naphthalene sulfonates, and alkali metal salts or alkaline earth metal salts of fatty acids, and neutral compounds such as alcohol alkoxylates (e.g., alcohol ethoxylates), phenol alkoxylates (e.g., tert-butylphenol ethoxylates or tert-pentylphenol ethoxylates), fatty acids, alkylphenols, condensation products of Ethylene Oxide (EO) and Propylene Oxide (PO) (e.g., in the form of block copolymers comprising EO/PO), polyethyleneimine or polysiloxanes.

Other suitable dehazing agents are EO/PO based alkoxylates of alkylphenol-formaldehyde condensates (of the Novolac (novolacs), resol (resol) or calixarene (calixarene) type), EO/PO based alkoxylates of diols (e.g. propylene glycol, ethylene glycol), triols (e.g. glycerol or trimethylolpropane), ethylenediamine or polyethyleneimine. Other suitable defogging agents are alkylbenzenesulfonic acids, dialkyl sulfosuccinates or alkali metal or ammonium salts thereof. Suitable demisting agents are described in WO 96/22343. Other suitable demisters based on diglycidyl ethers are described in US 3383326 and US 3511882.

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

Antioxidant agent

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, sterically hindered phenols containing ester groups, preferably having groups in the para-position, such as 3- [3, 5-di- (dimethylethyl) -4-hydroxy-phenyl ]]Propionic acid C ₆ -to C ₂₀ Alkyl esters, such as 2-ethylhexyl or stearyl esters, and phenylenediamines, such as N, N' -di-sec-butyl-p-phenylenediamine.

Metal passivating agent

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

Solvent(s)

Suitable solvents are, for example, nonpolar organic solvents, such as aromatic compounds and aliphatic hydrocarbons, such as toluene, xylene, white spirit and products under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), and polar organic solvents, such as alcohols, such as 2-ethylhexanol, 2-propylheptanol, decanol, isotridecyl alcohol and isoheptadecyl alcohol. The solvent is typically added to the fuel along with the above-described additives and co-additives (coadditive), which are intended to be dissolved or diluted for better handling.

Accordingly, another object of the present invention is a fuel additive package for a gasoline fuel comprising

At least one branched primary alkyl amine, said alkyl 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,

-at least one deposit control agent selected from the group consisting of

-a quaternary ammonium compound having a quaternary ammonium salt,

-mannich adducts, and

-a polyolefin monoamine or a polyolefin polyamine having a number average molecular weight in the range of 300 to 5000, and

-optionally at least one other gasoline fuel additive selected from the group consisting of

Friction modifier

- -demisting agent

Antioxidant agent

Metal deactivator

-a corrosion inhibitor,

- -carrier oil, and

-a solvent.

Preferably, the at least one other gasoline fuel additive is selected from the group consisting of corrosion inhibitors, carrier oils and solvents.

An advantage of the present invention is that the use of branched alkylamines can reduce the amount of solvent in the additive package as compared to the use of linear alkylamines.

Fuel and its production process

In the context of the present invention, gasoline fuel means liquid hydrocarbon distillate fuel boiling in the gasoline range. In principle, it is applicable to all types of petrol, including "light" and "heavy" petrol types. The gasoline fuel may also contain some other fuel, such as ethanol.

Furthermore, typically, the gasoline fuels that can be used according to the invention have one or more of the following characteristics:

the aromatic content of the gasoline fuel is preferably not more than 50% by volume, and more preferably not more than 35% by volume. The preferred range of aromatic content is from 1 to 45% by volume, and in particular from 5 to 35% by volume.

The sulfur content of the gasoline fuel is preferably not more than 100 ppm by weight, and more preferably not more than 10 ppm by weight. The preferred range of sulfur content is 0.5 to 150 ppm by weight, and in particular 1 to 10 ppm by weight.

The olefin content of the gasoline fuel is not more than 21% by volume, preferably not more than 18% by volume, and more preferably not more than 10% by volume. The preferred range of olefin content is from 0.1 to 21% by volume, and in particular from 2 to 18% by volume.

The benzene content of the gasoline fuel is not more than 1.0% by volume, and preferably not more than 0.9% by volume. The preferred range of benzene content is 0 to 1.0% by volume, and preferably 0.05 to 0.9% by volume.

The oxygen content of the gasoline fuel is not more than 45 wt%, preferably 0 to 45 wt%, and most preferably 0.1 to 3.7 wt% (first type) or most preferably 3.7 to 45 wt% (second type). The second type of gasoline fuel described above is a mixture of lower alcohols (e.g., methanol or, in particular, ethanol) preferably derived from natural sources such as plants, with mineral oil-based gasoline (i.e., universal gasoline prepared from crude oil). An example of such a gasoline is "E85", which is a mixture of 85% by volume ethanol with 15% by volume mineral oil based gasoline. Fuels containing 100% lower alcohols, particularly ethanol, are also suitable.

The amount of alcohol and ether contained in the gasoline can vary within wide limits. Typical maximum amounts are, for example, 15% by volume of methanol, 85% by volume of ethanol, 20% by volume of isopropanol, 15% by volume of tert-butanol, 20% by volume of isobutanol, and 30% by volume of ethers having 5 or more carbon atoms in the molecule.

The summer vapor pressure of gasoline fuels is typically no more than 70kPa, and preferably no more than 60kPa (at 37 ℃).

Gasoline fuels typically have a research octane number ("RON") of 90 to 100. The corresponding common range of engine octane number ("MON") is 80 to 90.

The above-mentioned properties are determined by conventional methods (DIN EN 228).

Accordingly, another object of the present invention is a gasoline fuel comprising

-at least one deposit control agent selected from the group consisting of

-a quaternary ammonium compound having a quaternary ammonium salt,

-mannich adducts, and

Friction modifier

- -demisting agent

Antioxidant agent

Metal deactivator

-a corrosion inhibitor,

- -carrier oil, and

-a solvent.

The gasoline fuel of the present invention comprises said at least one branched alkylamine in an amount of from 10 to 3000ppm, preferably from 15 to 1000ppm, more preferably from 20 to 500ppm, most preferably from 25 to 250ppm.

The deposit control agent or mixture of more than one such additive is present in the gasoline fuel in an amount typically in the range of from 10 to 1000ppm by weight, preferably from 25 to 500ppm by weight, more preferably from 50 to 250ppm by weight (based on the gasoline composition) in the case of polyolefin monoamines or polyolefin polyamines or mannich adducts.

In the case of quaternary ammonium compounds as deposit control agents, they are typically present in the gasoline fuel in an amount of from 10 to 100 ppm by weight, preferably from 20 to 50ppm by weight (based on the gasoline composition).

The one or more corrosion inhibitors, if any, are typically present in the gasoline fuel in an amount of from 0.1 to 10 ppm by weight, preferably from 0.2 to 8 ppm by weight, more preferably from 0.3 to 7 ppm by weight, most preferably from 0.5 to 5 ppm by weight, for example from 1 to 3 ppm by weight.

The carrier oil(s), if any, are typically present in the gasoline fuel in an amount of from 10 to 3000 ppm by weight, preferably from 20 to 1000 ppm by weight, more preferably from 50 to 700 ppm by weight, and most preferably from 70 to 500 ppm by weight.

The one or more dehazing agents, if any, are typically present in the gasoline fuel in an amount of from 0.5 to 100 ppm by weight, preferably from 1 to 50 ppm by weight, more preferably from 1.5 to 40 ppm by weight, most preferably from 2 to 30 ppm by weight, for example from 3 to 20 ppm by weight, as an additive component.

Each of the other additive components described above, if any, is typically present in the gasoline fuel in an amount of from 0.5 to 200 ppm by weight, preferably from 1 to 100 ppm by weight, more preferably from 1.5 to 40 ppm by weight, and most preferably from 2 to 30 ppm by weight.

The subject of the invention is also a fuel additive concentrate suitable for use in gasoline fuels, comprising

0.01 to 40 wt%, preferably 0.05 to 20 wt%, more preferably 0.1 to 10 wt% of at least one branched alkylamine;

10 to 70 wt%, preferably 15 to 60 wt%, more preferably 20 to 50 wt% of at least one deposit control agent;

0.25 to 5 wt%, preferably 0.5 to 5 wt%, more preferably 0.75 to 3.5 wt%, most preferably 1.0 to 2 wt% of at least one corrosion inhibitor;

0 to 80 wt%, preferably 5 to 60 wt%, more preferably 10 to 40 wt% of at least one carrier oil;

0 to 80 wt%, preferably 5 to 50 wt%, more preferably 10 to 40 wt% of at least one solvent or diluent; and

0 to 15 wt%, preferably 0.5 to 10 wt%, more preferably 1 to 8 wt%, most preferably 3 to 7 wt% of each of the other additive components described above, if any;

provided that the sum of the components is always 100%.

Unless otherwise indicated, the amounts given throughout refer to pure components excluding, for example, solvents.

Examples

Example 1: injector cleanliness was measured with a direct injection spark ignition engine.

1. Injector cleanliness of direct injection gasoline engines (direct injection spark ignition (dis) or Gasoline Direct Injection (GDI)): keep clean (Keep-clean) performance

The test method is a primary version of the upcoming CEC test for injector fouling of dis engines (TDG-F-113) and is disclosed by D.Weissenberger, J.Pilbeam, "Characterisation of Gasoline Fuels in a DISI Engine" on the lecture held at Technische Akademie Esslingen at month 6, 27 of 2017. The test engine was a 125kW VW EA 111.4L TSI engine. The test procedure is a steady state test at an engine speed of 2000rpm and a constant torque of 56 Nm.

The test procedure was performed using the following injectors: magneti Marelli 03C 906 036e. The reference oil RL-271 from Haltermann Carless was used as the engine oil.

2. Injector cleanliness of direct injection gasoline engines (direct injection spark ignition (dis) or Gasoline Direct Injection (GDI)): clean-up performance

In a dirty-up-clean-up (dirty-up) event, the engine is run for more than 48 hours using base fuel as described for the keep clean procedure (see above). The relative change in activation time was determined as described above for the keep clean test. The subsequent purging operation was performed for more than 10 hours using the base fuel with additive (additized). At the end of the test, 3 data points were determined within 15 minutes, the average of which gives the activation time at the end of the clean-up test. The test results of the purge are the relative changes in the activation time of the injector with respect to the average activation time measured at the end of the dirty phase.

The test was performed according to CEC RF-83mod compliant with EN 228 using a low sulfur Haltermann DISI TSI fuel compliant with EN 228.

The dirty stage uses fuel without additives and is run for 48 hours, and the clean up stage uses fuel with additives added for 10 hours.

In run 1, the fuel contained 300mg/kg PIBA ^* And 30mg/kg of linear dodecylamine.

In run 2, the fuel contained 300mg/kg PIBA ^* And 30mg/kg of branched tridecylamine, which is obtained from the corresponding tridecylalcohol isomeric mixture by amination and has a branching coefficient of 2.2 as determined in accordance with the procedure described above.

* Kerocom (R) PIBA (65% by weight solution of a polyisobutene amine based on highly reactive polyisobutene (after hydroformylation and amination) with Mn=1000 in an aliphatic hydrocarbon mixture)

Nozzle coking is measured as a change in the activation time (ti_l) of the injector, which is measured periodically during the test procedure. The aperture of the injector orifice is reduced due to nozzle coking, so the activation time is regulated by the Engine Control Unit (ECU). The activation time in milliseconds is read directly from the ECU by the ECU control software. The extension of the activation time is an indicator of nozzle coking. The test duration was 48 hours.

After a 30 minute run-in period, 3 data points of ti_l were determined over 15 minutes, the average of which gives the activation time at the beginning of the test. At the end of the test, 3 data points were determined within 15 minutes, the average of which gives the activation time at the end of the test. The test results are the relative change in the activation time ti—l of the injector.

Run 1 (for comparison) becomes dirty: 14.14% clearance: 92.3%

Run 2 (invention) dirty: 11.32% clearance: 104.25%

It can be readily seen that the additive package comprising branched alkylamines of the present invention exhibits at least the same activity, if not increased activity, in reducing injector nozzle fouling as compared to linear dodecylamine of the prior art.

Example 2: determination of storage stability of full formulation gasoline additive package

Three gasoline performance packages were formulated according to the following table. The carrier liquid used was propoxylated tridecanol derived from trimeric butenes (after hydroformylation and hydrogenation). In both cases a clear formulation was obtained.

* Propoxylated tridecanol derived from trimeric butenes (hydroformylation and after hydrogenation)

***WO 15/11402Synthesis example 2 of maleic anhydride with C ₂₀ -to C ₂₄ Copolymers of olefins

* Solvent(s)

All three formulations were stored at 40 ℃, room temperature and-20 ℃ for one week to evaluate their storage stability.

	Formulation 1	Formulation 2 (comparison)	Formulation 3 (comparison)
				+40℃	Liquid, homogeneous	Liquid, homogeneous	Liquid, homogeneous
Room temperature	Liquid, homogeneous	Deposit material	Liquid, homogeneous
				-20℃	Liquid, homogeneous	Near solid	Liquid, homogeneous

It can be readily seen that comparative formulation 2, which uses components of the same weight composition as formulation 1 of the present invention, has much poorer storage stability than formulation 1.

In order to give comparable storage stability, the amount of solvent has to be increased significantly (comparative formulation 3).

Claims

1. Use of branched primary alkylamines as fuel additives in gasoline, said alkyl groups having 8 to 22, preferably 10 to 17, more preferably 13 carbon atoms and having a functional group selected from the group consisting of alkyl groups, and alkyl groups ¹ At least 1.0, preferably 1.0 to 8.0, more preferably 1.5 to 7.0 branches as determined by H-NMR spectroscopy.

2. Use according to claim 1 as an additive in a unleaded gasoline composition comprising a major part of gasoline suitable for use in a spark ignition engine for reducing injector nozzle fouling in a direct injection spark ignition engine.

3. Use of branched primary alkylamines as additives in fuel additive packages for improving the storage stability and/or the formulability of fuel additive packages for gasoline, said alkyl groups having 8 to 22, preferably 10 to 17, more preferably 13 carbon atoms and having a functional group obtainable by ¹ At least 1.0, preferably 1.0 to 8.0, more preferably 1.5 to 7.0 branches as determined by H-NMR spectroscopy.

4. The use according to any one of the preceding claims, wherein the gasoline composition further comprises at least one deposit control agent selected from the group consisting of

-a quaternary ammonium compound, which is a compound,

mannich adducts, and

5. The use according to any one of the preceding claims, wherein the branched primary alkyl amine is selected from the group consisting of

-a group consisting of 2-propylheptanamine,

-a branched non-amine group, the branched non-amine group,

-branched tridecylamines, and

-branched heptadecylamine.

6. An unleaded gasoline composition comprising a major portion of gasoline, suitable for use in a spark ignition engine,

10 to 3000 ppm by weight, based on the gasoline composition, of branched primary alkylamines, said alkyl groups having 8 to 22, preferably 10 to 17, more preferably 13 carbon atoms and having a molecular weight distribution by ¹ At least 1.0, preferably 1.0 to 8.0, more preferably 1.5 to 7.0 branches as determined by H-NMR spectroscopy.

7. The unleaded gasoline composition of claim 6 further comprising at least one deposit control agent selected from the group consisting of

From 10 to 100 ppm by weight of quaternary ammonium compounds,

-10 to 1000 ppm by weight of a mannich adduct, and

-10 to 1000 ppm by weight of a polyolefin monoamine or a polyolefin polyamine having a number average molecular weight in the range of 300 to 5000.

8. The unleaded gasoline composition of claim 7, wherein the at least one deposit control agent has the formula

⁺ NR ¹ R ² R ³ R ⁴ A ^-

Wherein the method comprises the steps of

A ^- Represents anions, preferably carboxylate radicals R ⁵ COO ^- Or carbonate group R ⁵ O-COO ^- ，

And is also provided with

R ¹ 、R ² 、R ³ 、R ⁴ And R is ⁵ Independently of one another, are substituted or unsubstituted, organic residues having from 1 to 100 carbon atoms, preferably unsubstituted, linear 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 in particular from 1 to 20 carbon atoms,

R ⁵ can also be provided with 5 to 20Substituted or unsubstituted cycloalkyl or aryl residues of preferably 5 to 12 carbon atoms.

9. The unleaded gasoline composition of claim 7, wherein the at least one deposit control agent is obtainable by: the addition of a compound comprising at least one oxygen-or nitrogen-containing group which reacts with the anhydride and additionally at least one quaternizable amino group to the polycarboxylic anhydride compound and subsequent quaternization in the presence of an acid or in an acid-free manner, preferably quaternization with epoxide, in particular styrene or propylene oxide, or quaternization with carboxylic acid esters, for example dimethyl oxalate or methyl salicylate, in the absence of free acid.

10. The unleaded gasoline composition of claim 7, wherein the at least one deposit control agent has the formula

Wherein in the formula

11. The unleaded gasoline composition of claim 7, wherein the at least one deposit control agent has the formula

Wherein in the formula

r represents hydroxy-C ₁ -to C ₄ -alkyl, preferably 2-hydroxypropyl.

12. The unleaded gasoline composition of claim 7, wherein the at least one deposit control agent has the formula

Wherein in the formula

13. The unleaded gasoline composition of claim 7, wherein the at least one deposit control agent has the formula

Wherein in the formula

14. The unleaded gasoline composition of claim 7, wherein the at least one deposit control agent has the formula

Wherein in the formula

r represents C ₁ -to C ₄ -alkyl, preferably methyl, and

15. The unleaded gasoline composition of claim 7, wherein the at least one deposit control agent has the formula

Wherein in the formula

16. A fuel additive package for a gasoline fuel comprising

At least one branched primary alkyl amine, said alkyl having 8 to 22, preferably 10 to 17, more preferably 13 carbon atoms and having a moiety derived from a carboxylic acid or an amine derived from a carboxylic acid ¹ At least 1.0, preferably 1.0 to 8.0, more preferably 1.5 to 7.0 branches as determined by H-NMR spectroscopy,

-at least one deposit control agent selected from the group consisting of

-a quaternary ammonium compound having a quaternary ammonium salt,

-mannich adducts, and

-a corrosion inhibitor,

- -carrier oil, and

-a solvent.