WO2014184013A1

WO2014184013A1 - Amine mixture

Info

Publication number: WO2014184013A1
Application number: PCT/EP2014/059025
Authority: WO
Inventors: Harald Schwahn; Marc Walter; Boris Breitscheidel
Original assignee: Basf Se
Priority date: 2013-05-14
Filing date: 2014-05-05
Publication date: 2014-11-20
Also published as: KR20160009634A; SG11201507990WA; CA2908827A1; AU2014267558A1; EP2997087A1

Abstract

The invention relates to an amine mixture which contains (A) polyisobutene amines and (B) aliphatic amines, with a mixture of linear or branched alkyl groups having 17 and 21 and if appropriate 13, 25, 29 and/or 33 carbon atoms, and which can preferably be obtained by hydroformylation and subsequent reductive amination of a mixture consisting of the underlying polybutene or polyisobutene and a mixture of C_12- to C_32- olefins with ammonia or an amine. This amine mixture is suitable for cleaning inlet valves in suction pipe injecting SI engines, and injection nozzles in direct injecting SI engines, and for keeping them 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 is} a mixture of

(i) 0 to 20% by weight of linear or branched C 1-3 -alkyl radicals,

(ii) 50 to 99% by weight of linear or branched C 1-7 -alkyl radicals,

(Iii) 1 to 50 wt .-% of linear or branched C2i-alkyl radicals and (iv) 0 to 20% by weight of linear or branched alkyl radicals having 25

and / or 29 and / or 33 carbon atoms, the sum of the wt .-% of all radicals (i) to (iv) for R ⁴

100% by weight, and the variables R ² and R ^{3 have} the abovementioned meanings, the sum of the parts by weight of components (A) and (B) being 100 parts by weight, and preferably by Hydroformylation and subsequent reductive amination of a mixture of corresponding parts by weight of the underlying polybutene or polyisobutene and one of the variables R ⁴ originally the underlying mixture of C12 to C32 olefins with ammonia or an amine of the formula HNR ² R ³ available is.

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 clean intake valves in intake manifold injection 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 in unleaded Use 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 comprise polyisobutenylmonoamines or polyisobutenylpolyamines 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.

International patent application PCT / EP2012 / 072498 (3) describes an amine mixture of polyisobuteneamine and linear or branched C6- to C6-O-alkylamines, which is recommended for purifying inlet valves and injection nozzles in gasoline engines. As individual C6 to C6OO-alkylamine compounds to be used here, heptadecylamine and heneicosylamine are mentioned inter alia.

It has now been found that an amine mixture which, in addition to polyisobuteneamine, comprises a mixture of alkylamines which contain a linear or branched C 1-7 -alkyrest, alkylamines which contain a linear or branched C 2-4 -alkyl radical and, if appropriate, alkylamines which have a linear or branched chain C13 and / or C25 and / or C29 and / or C33-alkyl radical, is particularly advantageous for cleaning and keeping clean inlet valves and injectors in gasoline engines. The present invention thus relates to the initially defined amine mixture, hereinafter referred to as "amine mixture according to the invention".

Preferably, the amine mixture according to the invention by hydroformylation and subsequent reductive amination of a mixture of corresponding parts by weight of the underlying polybutene or polyisobutene and one of the variables R ⁴ originally underlying mixture of C12 to C32 olefins with ammonia or an amine of the formula HNR ² R ³ produced. As a result of the hydroformylation reaction, the olefins form as intermediates the corresponding oxo products, which generally represent aldehyde / alcohol mixtures.

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. 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 aminomethylene 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.

EP-A 244 616 (4) 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 HNR ² R ³ 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 (4).

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

[-CH2-0- -CH ₂₎ _q -CH 2 CH ₂ -OH, wherein q is an integer of 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. The hydroformylation of the mixture of polybutene or polyisobutene and C 12 to C 32 olefins is usually - according to the teaching of document (4) - with carbon monoxide / hydrogen in the presence of a suitable rhodium or cobalt catalyst at temperatures between 80 and 200 ° C and pressing up to 600 bar performed.

The reductive amination of the mixture formed in the hydroformylation of polybutene or polyisobutene and the C12 to C32 olefins oxo product, which is usually an aldehyde / alcohol mixture is usually carried out as described in document (4). This reaction with ammonia or amines of the formula NHR ² R ³ in a hydrogen atmosphere is carried out generally at temperatures of 80 to 200 ° C and pressures up to 600 bar, preferably 80 to 300 bar. Conveniently, the reaction is carried out in the presence of a customary hydrogenation catalyst, for example Raney nickel or Raney cobalt. The co-use of inert under the reaction conditions of organic solvents such as hydrocarbons may be advantageous, as will be explained below.

The oxoproduct component of polybutene or polyisobutene produced in the precursor in the mixture is usually - according to the teaching of (4) - by hydroformylation of 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 preparation of the oxo product instead of the described highly reactive polybutene or polyisobutene but also of 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.

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 Poly isobutenamins the general formula (la) R -CH ₂ -NR ² R ³ (la) in the Variable R ^{1 represents} a polybutyl or polyisobutyl radical derived from isobutene and 0 to 20% by weight of n-butene and the variables R ² and R ^{3 have} the abovementioned meanings, and

(B) 0.1 to 99.9, in particular 5 to 50, especially 10 to 30 parts by weight of an alipha containing amine of the general formula (II). Component (B) represents a mixture of aliphatic amines containing medium to longer chain linear or branched alkyl radicals in the range of 13 to 33 carbon atoms, each differing by 4 carbon atoms. In this case, the main constituent is an aliphatic amine having a linear or branched C 1-7 -alkyl radical. As a rule, an aliphatic amine with a linear or branched C21-alkyl radical is the second most strongly represented in the mixture. Branched alkyl radicals are preferred here.

The variable R ⁴ in the aliphatic amine (II) for component (B) represents a mixture of (i) 0 to 20 wt .-%, in particular 1 to 15 wt .-%, especially 2 to 10 wt .-% linear or preferably branched, in particular slightly branched C 13 -alkyl radicals,

(Ii) 50 to 99 wt .-%, in particular 55 to 85 wt .-%, especially 60 to 75 wt .-% linear or preferably branched, in particular slightly branched

Ci7 radicals,

(Iii) 1 to 50 wt .-%, in particular 5 to 35 wt .-%, especially 10 to 25 wt .-% linear or preferably branched, in particular slightly branched C2i-alkyl radicals and

(iv) from 0 to 20% by weight, in particular from 1 to 12% by weight, especially from 2 to 8% by weight, of linear or preferably branched, in particular slightly branched, alkyl radicals having 25 and / or 29 and / or 33 Carbon atoms, wherein the sum of the wt .-% of all residues (i) to (iv) for R ⁴ gives 100 wt .-%.

Each member of groups (i) to (iv) should have at least one species each in the amine mixture (B); However, it is also possible for there to be in each case a plurality of preferably isomeric species having a C 1-7 -alkyl radical and / or a C 2-5 -alkyl radical and also, if present, a C 13, C 25, C 29 and / or C 33 -alkyl radical.

In a preferred embodiment, the amine mixture according to the invention contains as component (B) an aliphatic amine of the formula R ⁴ -NH 2, in which the variable R ^{4 is} a mixture of slightly branched alkyl radicals (i) to (iv) which is a hydroformylated C 12- to C32 olefin mixture is based, which is obtained in the oligomerization of C ₄ - hydrocarbon streams referred. Place the residues of groups (i) to (iv) then in each case by hydroformylation to a methyl group extended trimer to heptameric butene structures.

By "slightly branched" is meant a mean degree of branching according to the iso index of from 1.2 to 3.0, in particular from 1.7 to 2.5. The degree of branching in the originally underlying C12 to C32 is generally After the oligomerization of C4 hydrocarbon streams, in particular the homogeneous or heterogeneously catalyzed oligomerization of technical C4 streams of 10 to 90% by weight of butane From 10 to 90% by weight of linear butenes (butene-1, cis- and trans-butene-2) and from 1 to 5% by weight of isobutene, for example of raffinate II, to essentially unbranched octenes and dodecenes This typical heterogeneous catalyst contains nickel.The oligomerization is usually at

Temperatures of 30 to 280 ° C and pressures of 10 to 300 bar performed. Such oligomerization reactions are described, for example, in WO 99/25668 (5). Typically, the C12 to C32 olefin mixtures used have densities in the

Range of 0.75 to 0.85 g / cm ³ and boiling ranges in the range of 220 to 350 ° C.

In the case of the reductive amination, inert organic solvents can be used under the reaction conditions. The concomitant use of such inert organic solvents is particularly useful if the proportion of

Component (B) relative to the proportion of component (A) is relatively low. Particularly suitable such inert organic solvents are 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. Advantageously, one uses commercially available, for example, under the names Solvent Naphtha or Solvesso® technical hydrocarbon mixtures. The solvents mentioned can usually be added already in the precursor of the hydroformylation.

Particular preference is given as at least one n- or iso-Cio to C-u-paraffin or a mixture of such paraffins or as inert organic solvents under the reaction conditions

• 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. Mixing 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 (6).

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.

When concomitant use of inert organic solvents under the reaction conditions, in particular also with the concomitant use of L1), L2) or mixtures of L1) and L2) in the Vol. -Mischungsverhältnis of 10:90 to 90:10, these are usually used in the wt . Amine mixture of (A) and (B) to solvent from 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 comprises, as predominant components (A), 0.1 to 99.9 parts by weight of a polyisobutenamine 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 2,500, 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 is} a mixture of

(i) from 0 to 20% by weight of linear or branched C 1-3 -alkyl radicals, (ii) from 50 to 99% by weight of linear or branched C 1-7 -alkyl radicals,

(Iii) 1 to 50 wt .-% of linear or branched C2i-alkyl radicals and

(iv) 0 to 20% by weight of linear or branched alkyl radicals having 25

100% by weight, and the variables R ² and R ^{3 have} the abovementioned meanings, the sum of the parts by weight of components (A) and (B) being 100 parts by weight, which is characterized in that a mixture of corresponding parts by weight of the underlying polybutene or polyisobutene and one of the variables R ⁴ originally based on the mixture of C 12 to C 32 olefins is hydroformylated and then with ammonia or an amine of the formula HNR ² R ³ reductive aminated. The amine mixture of the predominant components (A) and (B) according to the invention 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, which contains the amine mixture according to the invention, is also the subject of the present invention. Preferably, such a fuel composition has an alcohol content, in particular a content of C ₄ to C ₄ -alkanols such as methanol or in particular ethanol, of 0 to 100% by volume, particularly preferably more than 0 to 90% by volume, in particular 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) for cleaning and keeping intake valves intact in intake-manifold gasoline engines and of injection nozzles in direct injection gasoline engines is the subject of the present invention.

When operating a combustion engine with a fuel composition containing it, the amine mixture according to the invention exhibits a very good detersive effect. In addition to this effect in cleaning and keeping clean the intake valves, the injectors and the entire intake system of the engine, it also has a number of other beneficial effects as fuel additives: They reduce the valve sticking and / or improve the compatibility of detergents with carrier oils, especially Polyether and polyetheramine carrier oils, especially at low temperatures, and / or improve compatibility in fuel compositions containing a mineral fuel fraction and C 1 -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 - to 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 are all commercially available gasoline fuel compositions into consideration. A typical representative here is the market-standard base oil from 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 ROZ of the petrol fuel composition is usually 75 to 105. A usual range for the corresponding MOZ is 65 to 95. The specified specifications are determined by conventional methods (DIN EN 228).

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

Suitable Cr to C ₄ -alkanols are methanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and, in particular, ethanol; Mixtures of the stated C 1 -C ₄ -alkanols are also possible as low-alcohol fuel components. In addition to the said low alcohol fuel components, the fuel composition of the invention may also contain ethers having 5 or more carbon atoms, for example methyl tert-butyl ether, in the molecule in an amount up to 30 vol .-%.

The amine mixture according to the invention can be added to the fuel composition to be additive alone or mixed 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 usually 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 moiety selected from: (a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;

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;

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

Polyoxy-C 2 to C 4 -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;

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

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 from 85 to 20,000, especially from 1 13 to 10,000, especially from 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 radicals each have M _n = 300 to 5000, in particular 500 to 2500, especially 700 to 2300 , considering.

In addition, the amine mixture according to the invention can be combined with even more customary components and additives. For example, carrier oils based on minerals or on a synthetic basis without pronounced detergent action may be mentioned here.

Suitable mineral carrier oils are fractions obtained in petroleum processing, such as kerosene or naphtha, bright stock or base oils with viscosities such as 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 acid esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; as well as color substances (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 others mentioned Components or additives are added, if desired, in customary amounts.

The present invention will be explained in 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%, 70 g of a mixture of oligomeric butenes of the composition 6.8 wt .-% trimer, 69.8 wt .-% tetramer , 17.2% by weight of pentamer, 5.2% by weight of hexamer and 1.0 part by weight of heptamer (mean degree of branching according to Iso index: 2.1, density: 0.81 g / cm ³ ) by distilling off a fraction of the boiling range from 241 to 328 ° C. (atmospheric pressure) from the reaction batch of a nickel heterogeneously catalyzed oligomerization of a technical C ₄ carbon stream, 200 g of a solvent mixture of 80% by weight of Mihagol® M and 20% by weight. % Nessol LIAV® 230 and 2.8 g cobalt carbonyl catalyst were heated for 5 hours at 185 ° C in a 2.5 liter stirred 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 wt .-% acetic acid and the mixture washed neutral. The resulting oxo product was treated together with 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 was evaporated off and the solvent was distilled off.

Claims

claims

1 . Amine mixture, containing as the predominant components

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 Po - lyaminoalkylenreste, polyoxyalkylene, 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 can assume the value 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

R ⁴ -NR ² R ³ (II) in which the variable R ^{4 is} a mixture of (i) 0 to 20% by weight of linear or branched C 1-3 -alkyl radicals,

(ii) 50 to 99% by weight of linear or branched C 1-7 -alkyl radicals, (Iii) 1 to 50 wt .-% of linear or branched C2i-alkyl radicals and

(iv) 0 to 20% by weight of linear or branched alkyl radicals having 25

and / or 29 and / or 33 carbon atoms, where the sum of the wt .-% of all residues (i) to (iv) for R ⁴ gives 100 wt .-%, and the variables R ² and R ³ are as defined above have, wherein the sum of the parts by weight of the components (A) and (B) 100 parts by weight results.

Amine mixture according to claim 1, containing as predominant components

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

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

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 mixture of slightly branched alkyl radicals (i) to (iv) which is a hydroformylated C 12 to C32 olefin mixture, which is obtained in the oligomerization of C ₄ -Kohlen- hydrogen flows.

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), the sum of the Parts of components (A) and (B) are 100 parts by weight.

Amine mixture, containing as the predominant components

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

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

R ⁴ -NR ² R ³ (II) the variable R ^{4 is} a mixture of

0 to 20% by weight of linear or branched C 1-3 -alkyl radicals,

From 50 to 99% by weight of linear or branched C 1-7 -alkyl radicals, (Iii) 1 to 50 wt .-% of linear or branched C2i-alkyl radicals and

(iv) 0 to 20% by weight of linear or branched alkyl radicals having 25

and / or 29 and / or 33 carbon atoms, where the sum of the wt .-% of all residues (i) to (iv) for R ⁴ gives 100 wt .-%, and the variables R ² and R ³ are as defined above wherein the sum of the parts by weight of components (A) and (B) gives 100 parts by weight, obtainable by hydroformylation and subsequent reductive amination of a mixture of corresponding parts by weight of the underlying polybutene or polyisobutene and one of the variables R ⁴ originally based mixture of C12 to C32 olefins with ammonia or an amine of the formula HNR ² R ³ .

Process for the preparation of an amine mixture, which is used as the predominant components

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 Po - lyaminoalkylenreste, polyoxyalkylene, 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 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 (Ii)

R ⁴ -NR ² R ³ (II) in which the variable R ^{4 is} a mixture of

(i) 0 to 20% by weight of linear or branched C 1-3 -alkyl radicals,

(ii) 50 to 99% by weight of linear or branched C 1-7 -alkyl radicals,

(Iii) 1 to 50 wt .-% of linear or branched C2i-alkyl radicals and

(iv) 0 to 20% by weight of linear or branched alkyl radicals having 25

and / or 29 and / or 33 carbon atoms, where the sum of the wt .-% of all residues (i) to (iv) for R ⁴ gives 100 wt .-%, and the variables R ² and R ³ are as defined above have, wherein the sum of the parts by weight of the components (A) and (B) 100 parts by weight results, characterized in that one comprises a mixture of corresponding parts by weight of the underlying polybutene or polyisobutene and one of the variables R ⁴ initially based mixture of C 12 to C 32 olefins hydroformylated and then aminated with ammonia or an amine of the formula HNR ² R ³ reductively.

A fuel composition containing an amine mixture according to claims 1 to 7.

9. A fuel composition according to claim 8, which has an alcohol content of 0 to 100 vol .-% and is suitable for operating gasoline engines.

10. Use of an amine mixture according to claims 1 to 7 for cleaning and keeping clean intake valves in intake manifold injection gasoline engines and injectors in direct injection gasoline engines.