WO2013075978A1

WO2013075978A1 - Amine mixture

Info

Publication number: WO2013075978A1
Application number: PCT/EP2012/072498
Authority: WO
Inventors: Harald Schwahn; Marc Walter
Original assignee: Basf Se
Priority date: 2011-11-23
Filing date: 2012-11-13
Publication date: 2013-05-30
Also published as: JP2014533760A; EP2782985A1; BR112014012561A2; ZA201404493B; KR20140103978A; SG11201402422RA; CA2856684A1; CN103975046A; MX2014006055A; AU2012342721A1

Abstract

The invention relates to an amine mixture comprising (A) a polyisobutene amine PIB(CH₂)_x(OH)_m(NR²R³)_n, where PIB represents a structure derived from polybutene or polyisobutene, R² and R³stand for hydrogen, aliphatic or aromatic hydrocarbon residues, primary or secondary, aromatic or aliphatic aminoalkylene residues or polyaminoalkylene residues, polyoxyalkylene residues, heteroaryl or heterocyclylresidues and x=0 or 1, m=0 or 1 and n=1, 2 or 3 and (B) an aliphatic amine R⁴-NR²R³, where R4 is a C₆to C₆₀₀alkyl residue, obtainable by reductive amination of a mixture of (i) the oxoproduct occurring during the hydroformulation of polybutene or polyisobutene and an alkanol R⁴-OH, or (ii) the epoxide an an alkanol R⁴-OH occurring during the epoxidation of polybutene or polyisobutene, or (iii) the nitro compound occurring during the reaction of polybutene or polyisobutene with nitric oxide and an alkanol R⁴-OH having ammonia or an amine HNR²R³. Said amine mixture is suitable for cleaning inlet valves and injection nozzles in gasoline engines and keeping same clean.

Description

amine mixture

Description The present invention relates to an amine mixture which is used as predominant components

(A) 0.1 to 99.9 parts by weight of a polyisobutene amine of the general formula (I) PIB (CH ₂ ) x (OH) _m (NR ² R ³ ) n (I) in which the grouping PIB of 0 skeleton derived from polybutene or polyisobutene containing n-butene or one of isobutene and 0 to 20

Represents n-butene-derived polybutyl or polyisobutyl radical, the variables R ² and R ³ , which may be identical or different, denote hydrogen, aliphatic or aromatic hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkylene radicals or polyaminoalkyl radicals. radicals, polyoxyalkylene radicals, heteroaryl or heterocyclyl radicals, or together with the nitrogen atom to which they are attached form a ring in which further heteroatoms may be present, and the variable x is 0 or 1, the variable m den Value 0 or 1 and the variable n can assume the value 1, 2 or 3, wherein the polyisobuteneamine (I) has a number-average molecular weight of 300 to 2500, and

(B) 0.1 to 99.9 parts by weight of an aliphatic amine of the general formula (II) R ⁴ -NR ² R ³ (II) in which the variable R ⁴ denotes a linear or branched C6 to C6oo-alkyl radical and the variables R ² and R ^{3 have} the abovementioned meanings, the sum of the parts by weight of components (A) and (B) giving 100 parts by weight, and which by reductive amination of a mixture of corresponding parts by weight of (i) formed in the hydroformylation of polybutene or polyisobutene oxo product and an alkanol of the formula R ⁴ -OH or

(ii) the epoxide produced by the epoxidation of polybutene or polyisobutene and an alkanol of the formula R ⁴ -OH or

(iii) the nitro compound formed in the reaction of polybutene or polyisobutene with nitrogen oxides or mixtures of nitrogen oxides and oxygen and an alkanol of the formula R ⁴ -OH with ammonia or an amine of the formula HNR ² R ³ .

Furthermore, the present invention relates to a fuel composition containing this amine mixture, as well as the use of this amine mixture for cleaning and keeping intake valves clean in intake manifold gasoline engines and injectors in direct injection gasoline engines.

Mixtures of polyisobuteneamines and aliphatic amines are known in the art. They are used in particular as components in gasoline additive formulations. Thus, WO 03/076554 (1) teaches hydrocarbylamines having a number average molecular weight of 140 to 255 for the hydrocarbyl radical, for example linear alkylamines of the formula CH 3 (CH 2) _n NH 2 where n = 9 to 17, together with nitrogen-containing fuel detergents such as polyisobutene monoamines to use in unleaded petrol to reduce deposits in the injectors of direct injection internal combustion engines. However, the hydrocarbylamines and the nitrogen-containing fuel detergents are prepared separately and combined together in the additive formulation.

WO 2009/074608 (2) describes fuel additive formulations which contain polyisobutenyl monoamines or polyisobutenyl polyamines as nitrogen-containing dispersants, synthetic or mineral carrier oils and amines such as di-n-tridecylamine, hydrogenated tallow fatty amine or cocoamine. Such amines serve as enhancers in valve cleaning and valve maintenance in internal combustion engines. The nitrogen-containing dispersants and the amines are, however, prepared separately and combined only in the additive formulation.

The preparation of such relatively long-chain amines is usually carried out from the corresponding alcohols by a complex amination step with ammonia or non-ammonia. dermolekularen amines before they can be incorporated into the fuel additive formulations. If such amines are to be used in fuel additive formulations, the object is to provide a simpler and more cost-effective synthesis of these amines.

Accordingly, it has been found that the synthesis of such longer chain amines can be combined with the production of polyisobutene amines in a single reaction step, whereby the separate amination step of the alcohols to the longer chain amines can be saved.

The present invention thus relates to the amine mixture initially defined by its method of preparation, hereinafter referred to as "amine mixture according to the invention." Since a part of the described amine mixtures as substance mixtures - regardless of their method of preparation - represents new substances, such amine mixtures are also the subject of the present invention, below also referred to as "amine mixture according to the invention". The amine mixture according to the invention preferably contains 50 to 95 parts by weight, in particular 70 to 90 parts by weight of component (A) and 5 to 50 parts by weight, in particular 10 to 30 parts by weight of component (B), wherein the sum of parts by weight of components (A) and (B) is 100 parts by weight. If the group PIB for a from 0 to 20 wt .-%, in particular 0 to 5 wt .-%, especially 0 to 1 wt .-% of n-butene-containing polybutene or preferably polyisobutene derived skeleton, are in the case of x = 0, the hydroxyl groups (- OH) and / or the amino groups (-NR ² R ³ ) according to general formula (I) usually on the carbon atoms of the last isobutene unit in the polymer chain, usually on o, ß- and / or γ-carbon atom. Such groups PIB occur primarily in embodiments (ii) and (iii).

In the case of x = 1, PIB represents a polybutyl or polyisobutyl radical derived from isobutene and 0 to 20% by weight, in particular 0 to 5% by weight, in particular 0 to 1% by weight, of n-butene ( hereinafter referred to as R ¹ ) which carries only one amino group (-NR ² R ³ ) on the additional methylene grouping (n = 1). This aminomethyl-ene grouping is usually predominantly at the o and ß-carbon atom or preferably predominantly at the α-carbon atom of the last isobutene unit in the polymer chain. Such polybutyl or Polyisobutylreste R ¹ occur mainly in embodiment (i). EP-A 244 616 (3) describes the preparation of polybutyl and polyisobutylamines of the formula R ¹ -CH ² -NR ² R ³ by hydroformylation of polybutene or polyisobutene and subsequent reductive amination of the resulting oxo product with ammonia or amines in analogy to the embodiment (i) described. The meanings of the variables R ² and R ³ for the formulas determining the present invention are encompassed by the meanings of the variables R ² and R ³ as defined in (3).

The variables R ² and R ³ are identical or different for the present invention and are preferably hydrogen or linear or branched C 1 - to C 13 -alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. Butyl, iso-butyl, tert-butyl, n-pen- tyl, sec-pentyl, iso-pentyl, tert-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethyl-hexyl , n-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl or isotridecyl or radicals containing unsubstituted or alkyl-substituted amino groups and / or hydroxyl groups, such as -CH ₂ -CH ₂ - NH ₂ , -CH ₂ -CH ₂ -N (CH ₃ ) 2, -CH ₂ -CH ₂ -CH ₂ -NH ₂ , -CH ₂ -CH ₂ -CH ₂ -N (CH ₃ ) 2, [-CH ₂ -CH ₂ -NH-] p-CH ₂ -CH ₂ -NH ₂ , wherein p is an integer from 1 to 7, in particular from 1 to 3, -CH ₂ -CH ₂ -OH, -CH (CH ₃ ) -CH ₂ -OH or

[-CH 2 -CH 2 -O-) _q -CH 2 -CH 2 -OH, where q is an integer from 1 to 30.

Examples of suitable amines HNR ² R ³ are methylamine, dimethylamine, ethylamine, diethylamine, ethylmethylamine, n-propylamine, di-n-propylamine, iso-propylamine, diisopropylamine, n-butylamine, di-n-butylamine, n Butylmethylamine, iso-butylamine, diisobutylamine, tert-butylamine, di-tert-butylamine, 2-ethylhexylamine, 2-propylheptylamine, 1, 2-ethylenediamine, dimethylaminopropylamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Particularly preferably, both variables R ² and R ^{3 are} hydrogen, whereby the amine HNR ² R ³ denotes ammonia.

The variable R ¹ preferably represents a polybutyl or polyisobutyl radical derived from isobutene and 0 to 20% by weight, in particular 0 to 5% by weight, in particular 0 to 1% by weight, of n-butene, which is 20 to 176 , in particular 36 to 104, in particular contains 60 to 88 carbon atoms.

The polyisobuteneamine of the general formula (I) preferably has a number-average molecular weight of 500 to 1500, in particular from 900 to 1300. According to embodiment (i), the reductive amination of the mixture of the oxo product formed during the hydroformylation of polybutene or polyisobutene, which is generally an aldehyde / alcohol mixture, and the alcohol of the formula R ⁴ -OH is usually as described in document (3 ). This reaction with ammonia or amines of the formula NHR ² R ³ in a hydrogen atmosphere is generally carried out at temperatures of 80 to 200 ° C. and pressures of up to 600 bar, preferably 80 to 300 bar. It is expedient to work in the presence of a customary hydrogenation catalyst, for example Raney Nickel or Raney cobalt. The concomitant use of under the reaction conditions inert organic solvents such as hydrocarbons may be advantageous. The oxo product produced in a precursor is usually - according to the teaching of (3) - by hydroformylation of the polybutene or polyisobutene, which preferably has a high content of terminal double bonds (vinylidene double bonds), in particular at least 70%, especially at least 80% vinylidene Double bonds, prepared with carbon monoxide / hydrogen in the presence of a suitable rhodium or cobalt catalyst at temperatures between 80 and 200 ° C and pressures of up to 600 bar. However, in the preparation of the oxo product instead of the described highly reactive polybutene or polyisobutene, it is also possible to use moderately reactive or conventional polybutene or polyisobutene having a content of less than 70% terminal double bonds (vinylidene double bonds), for example 10 to less than 70% or 50 to less than 70%, go out. A preferred embodiment of the present invention is an amine mixture which is considered to be predominant components

(A) 0.1 to 99.9, in particular 50 to 95, especially 70 to 90 parts by weight of a polyisobutenamine of the general formula (Ia)

R is -CH ₂ -NR ² R ³ (Ia) in which the variable R ^{1 is} a polybutyl or polyisobutyl radical derived from isobutene and from 0 to 20% by weight of n-butene and the variables R ² and R ³ are as defined above have and

(B) 0.1 to 99.9, especially 5 to 50, especially 10 to 30 parts by weight of an aliphatic amine of the general formula (II) and by reductive amination of a mixture of corresponding parts by weight of the in the hydroformylation of polybutene or polyisobutene resulting oxo product and an alkanol of the formula R ⁴ -OH with ammonia or an amine of the formula HNR ² R ^{3 is} available.

According to embodiment (ii), the reductive amination of the mixture of the epoxide formed in the epoxidation of polybutene or polyisobutene and the alcohol of the formula R ⁴ -OH is usually carried out as described in EP-A 476 485 (4). This reaction with ammonia or amines of the formula NHR ² R ³ is generally carried out in bulk or in a solvent which is inert under the reaction conditions, for example dissolved in aliphatic or aromatic hydrocarbons. or in ethers, at elevated temperature, for example at the reflux of the respective solvent or in a pressure vessel. For a rapid and complete reaction, the presence of mostly stoichiometric amounts of water as catalyst has proved to be advantageous. Acid or Lewis acid compounds such as p-toluenesulfonic acid, carboxylic acids, boron trifluoride etherates, titanates or stannates can be used as additional catalysts. The epoxide produced in a precursor is usually - according to the teaching of (4) - by conventional epoxidizing agents such as m-chloroperbenzoic acid, tert-butyl hydroperoxide or peracetic acid, optionally in the presence of Übergangsmetallkatalysato- ren such as molybdenum or tungsten salts or complexes, from polybutene or polyisobutene, which preferably has a high content of terminal double bonds (vinylidene double bonds), in particular at least 70%, especially at least 80% vinylidene double bonds. However, in the production of the epoxide instead of the described highly reactive polybutene or polyisobutene, it is also possible to use medium-reactive or conventional polybutene or polyisobutene having a content of less than 70% terminal double bonds (vinylidene double bonds), for example 10 to less than 70% or 50 to less than 70%, go out. Usually, in the case of embodiment (ii), polyisobuteneamines (I) having a hydroxyl group (-OH) (m = 1) and having an amino group (-NR ² R ³ ) (n = 1) and without methylene grouping (x = 0) are obtained.

In accordance with embodiment (iii), the reductive amination of the mixture of the nitro compound formed in the reaction of polybutene or polyisobutene with nitrogen oxides or mixtures of nitrogen oxides and oxygen and the alcohol of the formula R ⁴ -OH is usually as described in WO 96/03367 (5). , WO 96/03479 (6) and WO 97/03946 (7). This reaction with ammonia or amines of the formula NHR ² R ³ is generally carried out as catalytic hydrogenation with hydrogen in the presence of hydrogenation catalysts, for example noble metal catalysts such as platinum, palladium, ruthenium, rhodium, osmium or iridium, Raney catalysts such as nickel, Cobalt, iron or copper, mixed catalysts containing, for example, nickel, zirconium, copper and molybdenum or copper, chromium, zinc and barium, or oxidic or sulfidic hydrogenation catalysts, at elevated temperatures, in particular at 150 to 220 ° C and hydrogen pressures of 1 to 300 bar and usually carried out in solvents such as hydrocarbons or ethers. The nitro compound produced in a precursor is usually - according to the teachings of documents (5) to (7) - by reacting nitrogen oxides, in particular nitrogen monoxide, nitrogen dioxide, dinitrogen trioxide and / or dinitrogen tetroxide, or mixtures of these nitrogen oxides and oxygen with polybutene or Polyisobutene, which preferably has a high content of terminal double bonds (vinylidene double bonds), in particular at least 70%, especially at least 80% of vinylidene the double bonds, having, unpressurized or under pressure, discontinuous or continuous and advantageously produced in inert organic solvents such as hydrocarbons, halogenated hydrocarbons, ethers, amides and / or esters. However, in the preparation of the nitro compound instead of the described highly reactive polybutene or polyisobutene, it is also possible to use medium-reactive or conventional polybutene or polyisobutene having a content of less than 70% terminal double bonds (vinylidene double bonds), for example 10 to less than 70% or 50 to less than 70%, go out. Usually, in the case of embodiment (iii), polyisobuteneamines (I) having no or one hydroxyl group (-OH) (m = 0 or 1) and having one to three amino groups (-NR ² R ³ ) (n = 1 to 3) and without Methylene grouping (x = 0).

In a preferred embodiment, the variable R ⁴ in the alkanols of the formula R ⁴ -OH and in the resulting aliphatic amines of component (B) denotes a linear or branched C 7 to C 23 alkyl radical or a polybutyl or polyisobutyl radical having from 24 to 600 carbon atoms , Particular preference is given to a branched C 7 - to C 13 -alkyl radical or a polybutyl or polyisobutyl radical having from 24 to 600, in particular from 28 to 176, especially from 32 to 88 carbon atoms. Examples of linear or branched C6 to C600-alkyl radicals, in particular C7 to C23 linear or branched alkyl radicals and polybutyl or polyisobutyl radicals having 24 to 600 carbon atoms are n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl,

3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1, 1-dimethylpentyl, 1, 2-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,5-dimethylpentyl, 2

Diethylpentyl, 3-diethylpentyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl,

4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1, 1-dimethylhexyl, 1, 2-dimethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2, 6-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, n-nonyl, isononyl, n-decyl, 1-propylheptyl, 2-propylheptyl, 3-propylheptyl, n-undecyl, n-dodecyl, n- Tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2, 4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, Cyclodecyl and a polyisobutyl radical having 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 76, 80, 84 or 88 carbon atoms.

Of course, one can also use a mixture of different alkanols of the formula R ⁴ -OH, which naturally results in a corresponding mixture of different aliphatic amines (II) in the component (B). In the reductive amination according to embodiments (i), (ii) and / or (iii), inert organic solvents may be included under the reaction conditions. The concomitant use of such inert organic solvents is particularly useful when the proportion of component (B) compared to the proportion of component (A) is relatively low. As such inert organic solvents are especially aliphatic, cycloaliphatic and aromatic hydrocarbons such as alkanes, eg. As n-pentane, n-hexane or n-heptane, or technical alkane mixtures, cyclohexane, cycloheptane, cyclooctane, toluene, xylenes, naphthalenes or tetrahydronaphthalene ("tetralin"), but also, for example, ethers such as diethyl ether, tert-butyl methyl ether or tetrahydrofuran are used. It is advantageous to use commercial hydrocarbon mixtures commercially available, for example, under the names Solvent Naphtha or Solvesso®. The abovementioned solvents can usually already be added in the precursors-ie in the hydroformylation in embodiment (i), in the epoxidation in embodiment (ii) and in the reaction with nitrogen oxides or nitrogen oxide / oxygen mixtures in embodiment (iii) become.

Particular preference is given to using organic solvents which are inert under the reaction conditions for the embodiment (ii), (iii) and especially for (i) either

• L1) at least one n- or iso-Cio to Ci ₄ paraffin or a mixture of such paraffins or

• L2) at least one C 10 to C ₄ -Naphthen or a mixture of such naphthenes or

A mixture of L1) and L2) in the vol. Mixture ratio of 10:90 to 90:10. The use of such inert organic solvents is described for the preparation of polyisobutene in WO 2004/087808 (8). Suitable paraffinic solvents L1) are, for example, the products sold under the name Mihagol® by BP Germany products, eg. B. Mihagol M with a proportion of n-paraffins with a chain length of 1 1 to 13 carbon atoms of at least 99 wt .-%. Suitable naphthenic solvents L2) are, for example, the products marketed under the name LIAV® by Fortum Oil and Gas, eg. B. Nessol LIAV 230 with predominant proportions of saturated cyclic aliphatics having a carbon number of 10 to 14. With concomitant use of inert organic solvents under the reaction conditions, especially with the concomitant use of L1), L2) or mixtures of L1) and L2) in the vol .Mixing ratio of 10:90 to 90:10, you put this in usually in the weight ratio amine mixture of (A) and (B) to solvent of 50 to 99: 1 to 50, in particular 55 to 90: 5 to 10, especially 60 to 75: 25 to 40 a

The present invention also provides a process for the preparation of an amine mixture, which is used as predominant components

(A) 0.1 to 99.9 parts by weight of a polyisobutene amine of the general formula (I)

PIB (CH ₂ ) x (OH) _m (NR ² R ³ ) n (I) in which the group PIB is a skeleton derived from 0 to 20% by weight n-butene-containing polybutene or polyisobutene or one of isobutene and 0 to 20% by weight of n-butene-derived polybutyl or polyisobutyl radical, the variables R ² and R ³ , which may be identical or different, represent hydrogen, aliphatic or aromatic hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkylene radicals or polyaminoalkyl radicals , Polyoxyalkylenreste, heteroaryl or Heterocyclylreste may stand, or together with the nitrogen atom to which they are attached, form a ring in which further heteroatoms may be present, and the variable x is the value 0 or 1, the variable m the value 0 or 1 and the variable n can take the value 1, 2 or 3, wherein the polyisobuteneamine (I) has a number average molecular weight of 300 to 2500, and

0.1 to 99.9 parts by weight of an aliphatic amine of the general formula (II)

R ⁴ -NR ² R ³ (II) in which the variable R ^{4 is} a linear or branched C6 to C6OO-alkyl radical and the variables R ² and R ^{3 have} the abovementioned meanings, the sum of the parts by weight the components (A) and (B) gives 100 parts by weight, contains, which is characterized in that a mixture of corresponding parts by weight

(i) of the hydroformylation of polybutene or polyisobutene

Oxoprodukte and an alkanol of the formula R ⁴ -OH or

(ii) the epoxide produced by the epoxidation of polybutene or polyisobutene and an alkanol of the formula R ⁴ -OH or (iii) the nitro compound formed in the reaction of polybutene or polyisobutene with nitrogen oxides or mixtures of nitrogen oxides and oxygen and an alkanol of Formula R ⁴ -OH with ammonia or an amine of the formula HNR ² R ³ reductively aminated.

Since a part of the amine mixtures described as mixtures of substances - regardless of their method of preparation - represents new substances, the present invention is also an amine mixture, which as the predominant components (A) 0.1 to 99.9 parts by weight of a polyisobutenamine of the general formula

PIB (CH ₂ ) x (OH) _m (NR ² R ³ ) in which the group PIB comprises a skeleton derived from 0 to 20% by weight of n-butene-containing polybutene or polyisobutene or one of isobutene and 0 to 20% by weight. represents polybutyl or polyisobutyl radical derived from n-butene, the variables R ² and R ³ , which can be identical or different, represent hydrogen, aliphatic or aromatic hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkylene radicals or polyaminoalkyl radicals, polyoxyalkylene radicals, Heteroaryl or Heterocyclylreste may stand, or together with the nitrogen atom to which they are attached form a ring in which further heteroatoms may be present, and the variable x is the value 0 or 1, the variable m is 0 or 1 and the variable n can assume the value 1, 2 or 3, the polyisobuteneamine (I) having a number-average molecular weight of 300 to 2500, and

(Β ') 0.1 to 99.9 parts by weight of an aliphatic amine of the general formula (II)

in which the variable R ¹⁴ denotes a linear or branched C 6 - to C 7 -alkyl radical and the variables R ² and R ^{3 have} the abovementioned meanings, the sum of the parts by weight of the components (A) and (Β ' ) 100 parts by weight results.

Preferably, this amine mixture contains as component (Β ') an aliphatic amine of the general formula (II) in which the variable R ¹⁴ denotes a branched C 6 - to Cg-alkyl radical and the variables R ² and R ^{3 in} each case denote hydrogen. This amine mixture particularly preferably contains, as component (Β '), an aliphatic amine of the general formula (II) in which the variable R ¹⁴ denotes a 2-ethylhexyl radical and the variables R ² and R ³ denote hydrogen in each case.

In particular, this amine mixture contains as component (A) a polyisobuteneamine of the general formula (Ia)

R is -CH ₂ -NR ² R ³ (Ia) in which the variable R ^{1 is} a polybutyl or polyisobutyl radical having a number average molecular weight of from 300 to 2,500 and derived from isobutene and from 0 to 20% by weight of n-butene; ² and R ³ each denote hydrogen, and as component (Β ') an aliphatic amine of the general formula (II) in which the variable R ¹⁴ denotes a 2-ethylhexyl radical and the variables R ² and R ³ also each denote hydrogen.

The amine mixture according to the invention from the predominant components (A) and (B) or (A) and (Β ') is outstandingly suitable as a fuel additive, in particular for cleaning and keeping intake valves intact in intake manifold injection gasoline engines and of injectors in direct injection gasoline engines. Therefore, a fuel composition, in particular a gasoline fuel composition containing the amine mixture according to the invention, also subject of the present invention. Preferably, such a fuel composition has an Al koholgehalt, in particular a content of C _r to C ₄ alkanols such as methanol or especially ethanol, from 0 to 100 vol .-%, more preferably from more than 0 to 90 vol .-%, in particular from 5 to 90 vol .-% , especially from 50 to 85 vol .-%, and is suitable for operating gasoline engines.

Furthermore, the use of the amine mixture according to the invention from the predominant components (A) and (B) or (A) and (Β ') for cleaning and keeping clean inlet valves in intake manifold injection gasoline engines and injectors in direct injection gasoline engines subject of the present invention.

When operating an internal combustion engine with a fuel composition containing it, the amine mixture according to the invention exhibits a very good detergency effect. In addition to this effect in the cleaning and keeping clean of the inlet valves, the injection nozzles and the entire intake system of the engine, it also exerts a number of other beneficial effects as fuel additives: they reduce valve sticking and / or improve the compatibility of the detergents with carrier oils. especially polyether and polyetheramine carrier oils, especially at low temperatures, and / or they improve the compatibility in fuel compositions containing a mineral fuel fraction and C _r C ₄ alkanols. Furthermore, fuel additive concentrates containing the amine mixture according to the invention, sufficiently low viscosity (ie they have a sufficiently low viscosity), so that capacity bottlenecks in the production of such fuel additive concentrates due to temporary flow rates through the equipment and lines - even with the concomitant use of inert Solvents or diluents - should be avoided; the comparatively low viscosity also has an unpredictable beneficial effect on the mode of action as fuel additives.

By fuel composition is to be understood in the context of the present invention preferably a gasoline fuel composition. As gasoline fuels all commercially available gasoline fuel compositions are considered. A typical representative here is the market-standard basic fuel of Eurosuper according to EN 228. Furthermore, gasoline compositions of the specification according to WO 00/47698 are also possible fields of use for the amine mixture according to the invention.

For example, a gasoline composition having an aromatic content of at most 60% by volume, such as a maximum of 42% by volume, and a sulfur content of at most 2000, such as e.g. maximum 150 ppm by weight, to name.

The aromatics content of the gasoline composition is preferably not more than 50% by volume, in particular from 1 to 45% by volume, especially from 5 to 40% by volume. The sulfur content of the gasoline is preferably at most 500 ppm by weight, in particular 0.5 to 150 ppm by weight, especially 1 to 100 ppm by weight.

Furthermore, the gasoline composition, for example, an olefin content up to 50 vol .-%, preferably from 0.1 to 21 vol .-%, in particular from 2 to 18% by volume, a benzene content of up to 5 vol .-%, preferably 0 to 1, 0 vol .-%, in particular 0.05 to 0.9 vol .-%, and / or an oxygen content of up to 47.5 wt .-%, such as 0.1 to 2.7 wt. % or, for example, from 2.7 to 47.5% by weight (for gasoline compositions containing predominantly lower alcohols).

In particular, those gasoline fuel compositions may also be mentioned by way of example, which at the same time has an aromatics content of not more than 38% by volume, an olefin content of not more than 21% by volume, a sulfur content of not more than 50 ppm by weight, a benzene content of not more than 1.0% by volume. -% and have an oxygen content of 0.1 to 47.5 wt .-%.

The summer vapor pressure of the gasoline composition is usually not more than 70 kPa, in particular 60 kPa (each at 37 ° C). The RON of the gasoline composition is typically 75 to 105. A typical range for the corresponding MOZ is 65 to 95.

The specified specifications are determined by conventional methods (DIN EN 228).

In addition to the use in gasoline fuels, however, it is also possible in principle to use the amine mixture according to the invention in other types of fuels or fuels, for example diesel fuels, kerosene or turbine fuels. A use in lubricant compositions is conceivable.

Suitable C _r to C ₄ -alkanols are methanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and, in particular, ethanol; Mixtures of said C _r C ₄ alkanols are possible as low alcohol fuel components. In addition to the abovementioned low-alcohol fuel components, the inventive fuel composition may also contain ethers having 5 or more carbon atoms, for example methyl tert-butyl ether, in the molecule in an amount of up to 30% by volume.

The amine mixture according to the invention can be added to the fuel composition to be additive alone or in admixture with other effective additive components (co-additives). As examples of such co-additives, there may be mentioned various additives having detergent action and / or having valve seat wear-inhibiting action (hereinafter collectively referred to as detergent additives) of the component (A) of the amine mixture of the present invention. Such a detergent additive generally has at least one hydrophobic hydrocarbon radical having a number-average molecular weight (M _n ) of from 85 to 20 000 and at least one polar group selected from:

(a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;

(b) nitro groups, optionally in combination with hydroxyl groups;

(c) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;

(d) carboxyl groups or their alkali metal or alkaline earth metal salts;

(e) sulfonic acid groups or their alkali metal or alkaline earth metal salts;

(f) polyoxy-C 2 to C 4 alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups; (g) carboxylic acid ester groups;

(h) succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups; and / or (i) moieties generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.

The hydrophobic hydrocarbon radical in the above detergent additives, which provides sufficient solubility in the fuel, has a number average molecular weight (M _n ) of 85 to 20,000, especially 1 13 to 10,000, especially 300 to 5,000. As a typical hydrophobic hydrocarbon radical , in particular in connection with the polar groups (a), (c), (h) and (i), the polypropenyl, polybutenyl and polyisobutenyl radical having in each case M _n = 300 to 5000, in particular 500 to 2500, especially 700 to 2300, into consideration.

In addition, the amine mixture according to the invention can be combined with even more customary components and additives. For example, carrier oils are present here mineral base or on synthetic basis without pronounced detergent action to call.

Suitable mineral carrier oils are fractions obtained in petroleum processing, such as kerosene or naphtha, bright stock or base oils having viscosities, for example from class SN 500 to 2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Also useful is a fraction known as "hydrocrack oil" and obtained in the refining of mineral oil (vacuum distillate cut having a boiling range of about 360 ° to 500 ° C., obtainable from high pressure, catalytically hydrogenated and isomerized and deparaffinated natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.

Examples of useful synthetic carrier oils can be selected from polyolefins (polyalphaolefins or polyinteralalefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-promoted polyetheramines and carboxylic acid esters of long-chain alkanols. Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers containing about 5 to 35 C3 to C6 alkylene oxide units, usually selected from propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof. Nonlimiting examples of starter alcohols suitable for this purpose are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical. Preferred examples of this are tridecanol and nonylphenol.

Further customary fuel additives are corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or of heterocyclic aromatics in the case of non-ferrous metal corrosion protection; Antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; demulsifiers; Antistatic agents; Metallocenes such as ferrocene; methylcyclopentadienyl; Lubricity additives such as certain fatty acids, alkenyl succinic esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; as well as dyes (markers). Optionally, amines are added to lower the pH of the fuel.

The components or additives mentioned can be added to the fuel composition individually or as a previously prepared concentrate (additive package) together with the amine mixture according to the invention. The amine mixture of the invention is the fuel composition - either separately or in the form of a concentrate with other components or additives and optionally conventional solvents and diluents - usually in an amount of 5 to 5000, preferably 10 to 2000, in particular 25 to 1000, before all 50 to 500 ppm by weight, in each case as pure substance indicated (ie without solvents and diluents and other components or additives) and based on the total amount of the fuel composition added. The other components or additives mentioned are, if desired, added in conventional amounts.

The present invention will be illustrated by the following example, which is not to be construed as limiting:

example

500 g of polyisobutene having a number average molecular weight of 1000 and a proportion of vinylidene double bonds of more than 70%, 200 g of a solvent mixture of 80% by weight of Mihagol® M and 20% by weight of Nessol LIAV® 230 and 2, 8 g of cobalt carbonyl catalyst were heated for 5 hours at 185 ° C in a 2.5 liter stirred-stroke autoclave with stirring at 280 bar carbon monoxide / hydrogen. Thereafter, the mixture was cooled to room temperature, the catalyst was removed with 400 ml of 10% strength by weight acetic acid and the mixture was washed neutral. The resulting oxo product was treated together with 75 g of 2-ethylhexanol, 1.0 liter of ammonia and 100 g of Raney cobalt in a 5 liter roll autoclave under a hydrogen pressure of 200 bar at 180 ° C. After cooling the mixture, the Raney cobalt catalyst was filtered off, excess ammonia evaporated and the solvent was distilled off.

Claims

claims

1 . Amine mixture containing as predominant components (A) from 0.1 to 99.9 parts by weight of a polyisobutene amine of the general formula (i)

PIB (CH ₂ ) x (OH) _m (NR ² R ³ ) n (I) in which the group PIB is a skeleton derived from 0 to 20% by weight n-butene-containing polybutene or polyisobutene or one of isobutene and Represents 0 to 20 wt .-% of n-butene derived polybutyl or Polyisobutylrest-, the variables R ² and R ³ , which may be identical or different, for hydrogen, aliphatic or aromatic hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkylene or polyaminoalkylene radicals, polyoxyalkylene radicals, heteroaryl or heterocyclyl radicals, or together with the nitrogen atom to which they are attached form a ring in which further heteroatoms may be present, and the variable x is 0 or 1 , the variable m is 0 or 1 and the

Variable n is 1,

May assume 2 or 3, wherein the polyisobuteneamine (I) has a number average molecular weight of 300 to 2500, and

(B) 0.1 to 99.9 parts by weight of an aliphatic amine of the general formula (Ii)

R ⁴ -NR ² R ³ (II) in which the variable R ⁴ denotes a linear or branched C 6 -C 6 -alkyl radical and the variables R ² and R ^{3 have} the abovementioned meanings, wherein the sum of the parts by weight of components (A) and (B) gives 100 parts by weight, obtainable by reductive amination of a mixture of corresponding parts by weight

(i) the oxo product formed in the hydroformylation of polybutene or polyisobutene and an alkanol of the formula R ⁴ -OH or

(ii) the epoxide formed in the epoxidation of polybutene or polyisobutene and an alkanol of the formula R ⁴ -OH or

Amine mixture according to claim 1, containing as predominant components

0.1 to 99.9 parts by weight of a polyisobutenamine of the general formula (Ia)

0.1 to 99.9 parts by weight of an aliphatic amine of the general formula (Ii) obtainable by reductive amination of a mixture of corresponding parts by weight of the oxo product formed in the hydroformylation of polybutene or polyisobutene and of an alkanol of the formula R ⁴ -OH with ammonia or an amine of the formula HNR ² R ³ .

3. Amine mixture according to claim 1 or 2, comprising as component (A) a polyisobuteneamine of the formula (I) or (Ia) having an average molecular weight of 500 to 1500.

An amine mixture according to claims 1 to 3, comprising as component (B) an aliphatic amine of the formula R ⁴ -NH 2 in which the variable R ^{4 is} a linear or branched C 7 - to C 23 -alkyl radical or a polybutyl or polyisobutyl radical having 24 to 600 Called carbon atoms.

An amine mixture according to claims 1 to 4, comprising 50 to 95 parts by weight, in particular 70 to 90 parts by weight of component (A) and 5 to 50 parts by weight, in particular 10 to 30 parts by weight of component ( B), wherein the sum of the parts by weight of components (A) and (B) gives 100 parts by weight.

6. A process for the preparation of an amine mixture, which as the predominant components

0.1 to 99.9 parts by weight of a polyisobutenamine of the general formula

PIB (CH ₂ ) x (OH) _m (NR ² R ³ ), in which the group PIB comprises a skeleton derived from 0 to 20% by weight n-butene-containing polybutene or polyisobutene or one of isobutene and 0 to 20 % By weight n-butene-derived polybutyl or polyisobutyl radical, the variables R ² and R ³ , which may be identical or different, represent hydrogen, aliphatic or aromatic hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkylene radicals or polyaminoalkylene radicals, Polyoxyalkylenreste, heteroaryl or heterocyclyl radicals may stand, or together with the nitrogen atom to which they are attached form a ring in which further heteroatoms may be present, and the variable x is 0 or 1, the variable m den Value 0 or 1 and the variable n can assume the value 1, 2 or 3, wherein the polyisobuteneamine (I) has a number-average molecular weight of 300 to 2500, and

R ⁴ -NR ² R ³ (II) in which the variable R ⁴ denotes a linear or branched C 6 to C 6 0 0 alkyl radical and the variables R ² and R ^{3 have} the abovementioned meanings, the sum of the parts by weight of Components (A) and (B) 100 parts by weight, contains, characterized in that a mixture of corresponding parts by weight

(iii) the nitro compound formed in the reaction of polybutene or polyisobutene with nitrogen oxides or mixtures of nitrogen oxides and oxygen and an alkanol of the formula R ⁴ -OH with ammonia or an amine of the formula HNR ² R ^{3 are} reductively aminated.

7. Amine mixture, containing as the predominant components (A) 0.1 to 99.9 parts by weight of a polyisobutene of the general formula

(I)

PIB (CH ₂ ) x (OH) _m (NR ² R ³ ) n (I) in which the group PIB is a skeleton derived from 0 to 20% by weight n-butene-containing polybutene or polyisobutene or one of isobutene and 0 to 20% by weight of n-butene-derived polybutyl or polyisobutyl radical, the variables R ² and R ³ , which may be identical or different, are known for may be hydrogen, aliphatic or aromatic hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkylene radicals or polyaminoalkylene radicals, polyoxyalkylene radicals, heteroaryl or heterocyclyl radicals, or together with the nitrogen atom to which they are attached form a ring in which further heteroatoms may be present, and the variable x may be 0 or 1, the variable m may be 0 or 1, and the variable n may be 1, 2 or 3, the polyisobuteneamine (I) having a number average molecular weight of 300 to 2500, and

0.1 to 99.9 parts by weight of an aliphatic amine of the general formula (I i)

in which the variable R ¹⁴ denotes a linear or branched C 6 - to Cg-alkyl radical and the variables R ² and R ^{3 have} the abovementioned meanings, the sum of the parts by weight of the components (A) and (Β ') being 100 Parts by weight results.

8. amine mixture according to claim 7, comprising as component (Β ') an aliphatic amine of the general formula (II), in which the variable R ^{14 is} a branched C6 bis

Cg-alkyl radical and the variables R ² and R ³ each denote hydrogen.

9. amine mixture according to claim 8, comprising as component (Β ') an aliphatic amine of the general formula (II), in which the variable R ^{14 is} a 2-ethylhexyl radical and the variables R ² and R ^{3 are} each hydrogen.

10. amine mixture according to claim 9, comprising as component (A) a polyisobuteneamine of the general formula (Ia)

R is -CH ₂ -NR ² R ³ (Ia) in which the variable R ^{1 is} a radical derived from isobutene and from 0 to 20% by weight of n-butene. represents polybutyl or polyisobutyl radical having a number average molecular weight of 300 to 2500 and the variables R ² and R ³ each denote hydrogen, and as component (Β ') an aliphatic amine of the general formula (II), in which the variable R ^{14 is} a 2-ethylhexyl radical and the variables R ² and R ³ also each denote hydrogen.

1 1. A fuel composition containing an amine mixture according to claims 1 to 10.

12. A fuel composition according to claim 1 1, which has an alcohol content of 0 to 100 vol .-% and is suitable for operating gasoline engines.

13. Use of an amine mixture according to claims 1 to 10 for cleaning and keeping clean inlet valves in intake manifold injection gasoline engines and injectors in direct injection gasoline engines.