JP2014533760A - Amine mixture - Google Patents

Abstract

(A) Polyisobuteneamine PIB (CH2) x (OH) m (NR2R3) n (wherein PIB represents polybutene or a skeleton derived from polyisobutene or a polybutyl group or polyisobutyl group, and R2 and R3 represent hydrogen, fat, Aromatic hydrocarbon group or aromatic hydrocarbon group, primary or secondary aromatic aminoalkylene group or aliphatic aminoalkylene group, or primary or secondary aromatic polyaminoalkylene group or aliphatic polyaminoalkylene group And represents a polyoxyalkylene group, heteroaryl group or heterocyclyl group, and x is 0 or 1, m is 0 or 1, and n is 1, 2 or 3] and (B) Containing an aliphatic amine R4-NR2R3, wherein the substituent R4 is a C6-C600 alkyl group, An oxo product formed during the hydroformylation of a pentene or polyisobutene and an alkanol of formula R4-OH or (ii) an epoxide generated during the epoxidation of a polybutene or polyisobutene and an alkanol of formula R4-OH or (iii) a polybutene or polyisobutene The invention relates to an amine mixture obtained by reductive amination of a mixture of a nitro compound produced during the reaction with nitrogen oxides and an alkanol of the formula R4-OH with ammonia or an amine of the formula HNR2R3. The amine mixture is suitable for cleaning and keeping the intake valves and injection nozzles in an Otto engine clean.

Description

As the main component of the present invention,
(A) General formula (I)
PIB (CH ₂ ) _x (OH) _m (NR ² R ³ ) _n (I)
[Where,
The PIB moiety represents a skeleton derived from polybutene or polyisobutene containing 0 to 20% by mass of n-butene or a polybutyl group or polyisobutyl group derived from isobutene and 0 to 20% by mass of n-butene,
The substituents R ² and R ³ may be the same or different, and may be hydrogen, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, a primary or secondary aromatic aminoalkylene group or an aliphatic amino group. An alkylene group or a primary or secondary aromatic polyaminoalkylene group or an aliphatic polyaminoalkylene group, a polyoxyalkylene group, a heteroaryl group or a heterocyclyl group, or a nitrogen atom to which they are bonded Together with a ring, there may still be heteroatoms in the ring, and the variable x can have a value of 0 or 1, and the variable m has a value of 0 or 1. And the variable n can take a value of 1, 2 or 3) 0.1-99.9 parts by weight of polyisobuteneamine
In that case, the polyisobutenamine (I) has a number average molecular weight of 300 to 2500,
And (B) general formula (II)
R ⁴ —NR ² R ³ (II)
[Wherein, the substituent R ⁴ represents a linear or branched C ₆ -C ₆₀₀ alkyl group,
And R ² and R ^{3 as} substituents have the above meanings], and an amine mixture containing 0.1 to 99.9 parts by mass of an aliphatic amine.
In this case, the sum of the parts by weight of components (A) and (B) is 100 parts by weight, and (i) the oxo product produced during the hydroformylation of polybutene or polyisobutene and the alkanol of formula R ⁴ —OH or (Ii) epoxides produced during the epoxidation of polybutene or polyisobutene and alkanols of the formula R ⁴ —OH or (iii) nitro produced during the reaction of polybutene or polyisobutene with a mixture of nitrogen oxides or nitrogen oxides and oxygen It relates to said amine mixture, obtained by reductive amination of a corresponding part by weight of a compound 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 provides a fuel composition containing the amine mixture, and the use of the amine mixture for cleaning and keeping the intake valve in an intake pipe injection otto engine and the injection nozzle in a direct injection otto engine. About.

Mixtures of polyisobuteneamines and aliphatic amines are known from the state of the art. Said mixture is used in particular as a component in an Otto fuel additive formulation. That is, WO 03/075554 (1) describes hydrocarbylamines having a number average molecular weight of 140 to 255 relative to hydrocarbyl groups, for example to reduce deposits in the injection nozzle of a direct injection internal combustion engine, such as the formula A linear alkylamine of CH ₃ (CH ₂ ) _n NH ₂ , where n is 9-17, is used in a lead-free otto fuel together with a nitrogen-containing fuel detergent, such as polyisobutene monoamine. Is taught. However, the hydrocarbylamine and the nitrogen-containing fuel detergent are manufactured separately and are combined together only when fed into the additive formulation.

  WO 2009/074608 (2) describes polyisobutenyl monoamines or polyisobutenyl polyamines as nitrogen-containing dispersants, synthetic carrier oils or mineral carrier oils and amines such as di-n-tridecylamine, hydrogenation Fuel additive formulations containing tallow amine or coconut amine are described. This type of amine is used as a reinforcing agent for cleaning the valve and maintaining the valve in an internal combustion engine. However, the nitrogen-containing dispersant and the amine are manufactured separately and are first fed together in the additive formulation.

  This type of long chain amine is usually produced from the corresponding alcohol by an expensive amination process with ammonia or a lower amine, after which the long chain amine is added to the fuel additive formulation. sell. When this type of amine is shared in a fuel additive formulation, the challenge is to provide a simpler and cheaper synthesis for that amine.

  Accordingly, the synthesis of this type of long chain amine can be combined with the production of polyisobuteneamine in a single reaction step, thereby saving a separate amination step of the alcohol to the long chain amine. Was found.

  The subject of the present invention is thus the amine mixture defined by its form of manufacture, as mentioned at the outset, hereinafter referred to as “amine mixture according to the invention”.

  Since a portion of the amine mixture described produces a new substance as a substance mixture--regardless of its form of production--the amine mixture is also the subject of the present invention, hereinafter also according to the invention This is referred to as an “amine mixture”.

  The amine mixture according to the invention contains in particular 50 to 95 parts by weight of component (A), in particular 70 to 90 parts by weight and 5 to 50 parts by weight, in particular 10 to 30 parts by weight of component (B). The sum of the parts by mass of components (A) and (B) is 100 parts by mass.

When x is 0 when the PIB part represents a skeleton derived from polybutene or in particular polyisobutene containing 0 to 20% by weight, in particular 0 to 5% by weight, in particular 0 to 1% by weight of n-butene In addition, the hydroxyl group (—OH) and / or amino group (—NR ² R ³ ) according to the general formula (I) is usually on the carbon atom of the last isobutene unit in the polymer chain, often an α-carbon atom. Above, on the β-carbon atom and / or on the γ-carbon atom. This type of PIB moiety occurs especially in the case of embodiments (ii) and (iii).

When x is 1, PIB represents a polybutyl group or a polyisobutyl group derived from isobutene and n-butene from 0 to 20% by mass, in particular from 0 to 5% by mass, especially from 0 to 1% by mass (hereinafter, R ¹ ), the group merely has an amino group (—NR ² R ³ ) on the further methylene moiety (n = 1). This aminomethylene moiety is usually present mainly on the [alpha] -carbon atom and [beta] -carbon atom of the last isobutene unit in the polymer chain or especially mainly on the [alpha] -carbon atom. This type of polybutyl or polyisobutyl group R ¹ occurs especially in the case of embodiment (i).

EP-A-244616 (3) contains, as in embodiment (i), by hydroformylating polybutene or polyisobutene and subsequently reductively aminating the resulting oxo product with ammonia or amines. The preparation of polybutylamine and polyisobutylamine of the formula R ¹ —CH ₂ —NR ² R ³ is described. The meanings of R ² and R ³ as substituents for the formulas defining the present invention are included by the meaning of R ² and R ³ as substituents, as defined in (3).

The substituents R ² and R ³ are identical or different with respect to the invention and are especially hydrogen or a linear or branched C ₁ -C ₁₃ alkyl group such as methyl, ethyl, n- Propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, s-pentyl, isopentyl, t-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl or isotridecyl or unsubstituted amino group or alkyl-substituted amino group and / or unsubstituted hydroxyl group or alkyl-substituted hydroxyl Groups containing 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 , where p represents an integer of 1 to 7, in particular 1 to 3, and represents —CH ₂ —CH ₂ —OH, —CH (CH ₃ ) —CH ₂ —OH or [ _{-CH 2 -CH 2 -O-] q -CH} 2 -CH 2 -OH, wherein, q represents the, and represents 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, isopropylamine, di-isopropylamine, n-butylamine. , Di-n-butylamine, n-butylmethylamine, isobutylamine, di-isobutylamine, t-butylamine, di-t-butylamine, 2-ethylhexylamine, 2-propylheptylamine, 1,2-ethylenediamine, dimethylamino Propylamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Particularly preferably, the two substituents R ² and R ³ represent hydrogen, whereby the amine HNR ² R ³ is called ammonia.

The substituent R ¹ represents in particular a polybutyl or polyisobutyl group derived from isobutene and n-butene from 0 to 20% by weight, in particular from 0 to 5% by weight, in particular from 0 to 1% by weight, these groups being 20 to 176, in particular 36 to 104, in particular 60 to 88 carbon atoms.

  The polyisobuteneamines of the general formula (I) have a number average molecular weight of 500 to 1500, in particular 900 to 1300, among others.

According to embodiment (i), the reductive amination of a mixture of an oxo product, typically an aldehyde / alcohol mixture, and an alcohol of formula R ⁴ —OH, which occurs during the hydroformylation of polybutene or polyisobutene, is usually It is carried out in the same manner as described in the literature (3). In so doing, the reaction with ammonia or amines of the formula NHR ² R ³ in a hydrogen atmosphere is generally carried out at a temperature of from 80 to 200 ° C. and up to 600 bar, in particular at a pressure of from 80 to 300 bar. Preferably, the operation is carried out in the presence of a conventional hydrogenation catalyst such as Raney nickel or Raney cobalt. It is preferred to share an organic solvent that is inert under the reaction conditions, such as hydrocarbons. The oxo products formed with the precursors are usually-according to the teaching of (3)-especially with a high content of terminal double bonds (vinylidene double bonds), in particular at least 70%, in particular at least 80%. It is prepared by hydroformylation of polybutenes or polyisobutenes having vinylidene double bonds with carbon monoxide / hydrogen in the presence of a suitable rhodium or cobalt catalyst at temperatures of 80-200 ° C. and pressures up to 600 bar. However, when producing oxo products, instead of the highly reactive polybutene or polyisobutene described, the terminal double bond (vinylidene double bond) is less than 70%, for example less than 10-70% or 50 It is also possible to start with moderately reactive or normal polybutenes or polyisobutenes with a content of less than ˜70%.

Preferred embodiments for the present invention are:
(A) General formula (Ia)
R ¹ —CH ₂ —NR ² R ³ (Ia)
[Wherein, the substituent R ¹ represents a polybutyl group or a polyisobutyl group derived from 0 to 20% by mass of isobutene and n-butene, and the substituents R ² and R ³ have the above-mentioned meanings] 0.1-99.9 parts by weight of polyisobuteneamine, in particular 50-95 parts by weight, in particular 70-90 parts by weight and (B) 0.1-99.9 parts of the aliphatic amine of the general formula (II). Parts by weight, in particular from 5 to 50 parts by weight, in particular from 10 to 30 parts by weight, and corresponding parts by weight of the oxo product and the alkanol of the formula R ⁴ —OH produced during the hydroformylation of polybutene or polyisobutene. An amine mixture obtained by reductive amination of the mixture with ammonia or an amine of the formula HNR ² R ³ .

According to embodiment (ii), the reductive amination of a mixture of an epoxide and an alcohol of the formula R ⁴ —OH formed during the epoxidation of polybutene or polyisobutene is described in EP-A 476 485 (4). The same as described above. In so doing, the reaction with the ammonia or amine of the formula NHR ² R ³ is usually in bulk or in an inert solvent under the reaction conditions, for example in aliphatic or aromatic hydrocarbons or in ethers. In an elevated temperature, for example under reflux of the respective solvent or in a pressure vessel. For rapid and complete reactions, the presence of usually stoichiometric amounts of water as a catalyst has proven favorable. In addition, acidic or Lewis acid compounds such as p-toluenesulfonic acid, carboxylic acid, boron trifluoride etherate, titanate or stannate can be used as catalysts to be used. The epoxide formed with the precursor is usually-according to the teaching of (4)-optionally with a transition metal catalyst, by a conventional epoxidizing agent such as m-chloroperbenzoic acid, t-butyl hydroperoxide or peracetic acid, For example, in the presence of molybdate or tungstate or molybdate or tungstate complexes, in particular a high content of terminal double bonds (vinylidene double bonds), in particular at least 70% vinylidene double bonds, in particular at least 80 % Polybutene or polyisobutene. However, when producing the epoxide, instead of the highly reactive polybutene or polyisobutene described, the terminal double bond (vinylidene double bond) is less than 70%, such as less than 10-70% or 50-70. It is also possible to start with moderately reactive or normal polybutenes or polyisobutenes with a content of less than%.

Usually, in the case of embodiment (ii), it has one hydroxyl group (—OH) (m = 1) and one amino group (—NR ² R ³ ) (n = 1). And polyisobuteneamine (I) which does not have a methylene group (x = 0) is obtained.

According to embodiment (iii), polybutenes or polyisobutenes and nitrogen oxides or nitrogen oxidations are generally as described in WO 96/03367 (5), WO 96/03479 (6) and WO 97/03946 (7). The reductive amination of a mixture of a nitro compound and an alcohol of the formula R ⁴ —OH produced during the reaction with a mixture of product and oxygen is carried out. In doing so, the reaction with ammonia or amine of the formula NHR ² R ³ is usually carried out as a catalytic hydrogenation with hydrogen, as a hydrogenation catalyst such as a noble metal catalyst such as platinum, palladium, ruthenium, rhodium, osmium or iridium, lannies. The presence of catalysts, such as nickel, cobalt, iron or copper, mixed catalysts, such as nickel, zirconium, copper and molybdenum or mixed catalysts containing copper, chromium, zinc and barium, or oxide hydrogenation catalysts or sulfide hydrogenation catalysts Below, it is carried out at elevated temperatures, in particular at 150 to 220 ° C. and a hydrogen pressure of 1 to 300 bar, and usually in solvents, for example in hydrocarbons or ethers. The nitro compounds formed with the precursors are usually according to the teachings of the literature (5) to (7)-nitrogen oxides, in particular nitric oxide, nitrogen dioxide, anhydrous nitrous acid (Distickstoffrioxid) and / or tetroxide. Dinitrogen, or a mixture of these nitrogen oxides and oxygen, with a particularly high content of terminal double bonds (vinylidene double bonds), in particular at least 70%, in particular at least 80% vinylidene double bonds Polybutene or polyisobutene at normal pressure or under pressure, discontinuously or continuously, and preferably in inert organic solvents such as hydrocarbons, halogenated hydrocarbons, ethers, amides and / or esters It is manufactured by making it react with. However, when producing nitro products, instead of the highly reactive polybutene or polyisobutene described, the terminal double bond (vinylidene double bond) is less than 70%, for example less than 10-70% or 50 It is also possible to start with moderately reactive or normal polybutenes or polyisobutenes with a content of less than ˜70%.

Usually, in the case of embodiment (iii), it has no hydroxyl group (—OH) (m = 0) or one hydroxyl group (—OH) (m = 1) and 1 to 3 The polyisobuteneamine (I) having the amino group (—NR ² R ³ ) (n = 1 to 3) and no methylene group (x = 0) is obtained.

In a preferred embodiment, wherein R ⁴ -OH substituents R ⁴ of the aliphatic amine of occurrence of alkanol and component (B) of, C ₇ -C ₂₃ alkyl or 24 to a linear or branched Represents a polybutyl or polyisobutyl group having 600 carbon atoms. Particular preference is given to branched C ₇ -C ₁₃ alkyl groups or polybutyl or polyisobutyl groups having 24 to 600, in particular 28 to 176, in particular 32 to 88 carbon atoms. Linear or branched C ₆ -C ₆₀₀ alkyl groups, in particular linear or branched C ₇ -C ₂₃ alkyl groups and polybutyl or polyisobutyl having 24 to 600 carbon atoms Examples of groups 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, cyclohex , 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethyl Cyclohexyl, 3,5-dimethylcyclohexyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and 24, 28, 32, 36, 40, 44 Polyisobutyl groups having 48, 52, 56, 60, 64, 68, 72, 76, 80, 84 or 88 carbon atoms.

Of course, mixtures of various alkanols of the formula R ⁴ —OH may be used, which inevitably results in corresponding mixtures of various aliphatic amines (II) in component (B).

  In the case of reductive amination according to embodiments (i), (ii) and / or (iii), an organic solvent which is inert under the reaction conditions can be shared. The use of the inert organic solvent is particularly advantageous when the proportion of component (B) is relatively small compared to the proportion of component (A). As inert organic solvents of this kind, inter alia aliphatic hydrocarbons, cycloaliphatic hydrocarbons and aromatic hydrocarbons such as alkanes such as n-pentane, n-hexane or n-heptane, or industrial alkane mixtures, cyclohexane , Cycloheptane, cyclooctane, toluene, xylene, naphthalene or tetrahydronaphthalene (“tetralin”) are suitable, but other than that, for example, ethers such as diethyl ether, t-butyl methyl ether or tetrahydrofuran may be used. Good. Preferably, industrial hydrocarbon mixtures are used which are available on the market, for example under the name Solvent Naphtha or Solvesso®. The solvents described are usually already precursors—that is, in the hydroformylation in the case of embodiment (i), in the epoxidation in embodiment (ii) and in the nitrogen oxide in embodiment (iii) Alternatively, it can be added in the reaction with a nitrogen oxide / oxygen mixture.

Particularly advantageously, for embodiments (ii), (iii) and especially (i), as organic solvent inert under the reaction conditions,
- L1) at least one n-C ₁₀ -C ₁₄ paraffin or iso C ₁₀ -C ₁₄ paraffin or a mixture of the paraffin, or - L2) at least one C ₁₀ -C ₁₄ naphthene, or mixtures of such naphthenic, or - 10 A mixture of L1) and L2) at a volume mixing ratio of 90:90:10 is used. The use of this type of inert organic solvent is described in connection with the production of polyisobutene in WO 2004/087808 (8).

  Suitable paraffinic solvents L1) are, for example, products sold by the company BP Deutschland under the name Mihagor®, for example n-paraffins having a chain length of 11-13 carbon atoms of at least 99% by weight. Mihagor M having a ratio of

  Suitable naphthenic solvents L2) are, for example, products sold by the company Fortum Oil and Gas under the name LIAV®, for example a large proportion of saturated cyclic fats having 10 to 14 carbon atoms. Nessol LIAV 230 with a family compound.

  In the case of sharing an inert organic solvent under the reaction conditions, in particular when L1), L2) or a mixture of L1) and L2) at a volume mixing ratio of 10:90 to 90:10 is also used, The organic solvent is usually in a mass ratio of amine mixture consisting of (A) and (B) of from 50 to 99: 1 to 50, in particular from 55 to 90: 5 to 10, in particular from 60 to 75:25 to 40, by weight. used.

The subject of the present invention is
(A) General formula (I)
PIB (CH ₂ ) _x (OH) _m (NR ² R ³ ) _n (I)
[Where,
The PIB moiety represents a skeleton derived from polybutene or polyisobutene containing 0 to 20% by mass of n-butene or a polybutyl group or polyisobutyl group derived from isobutene and 0 to 20% by mass of n-butene,
The substituents R ² and R ³ may be the same or different, and may be hydrogen, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, a primary or secondary aromatic aminoalkylene group or an aliphatic amino group. An alkylene group or a primary or secondary aromatic polyaminoalkylene group or an aliphatic polyaminoalkylene group, a polyoxyalkylene group, a heteroaryl group or a heterocyclyl group, or a nitrogen atom to which they are bonded Together with a ring, there may still be heteroatoms in the ring, and the variable x can have a value of 0 or 1, and the variable m has a value of 0 or 1. And the variable n can take a value of 1, 2 or 3) 0.1-99.9 parts by weight of polyisobuteneamine
In that case, the polyisobutenamine (I) has a number average molecular weight of 300 to 2500,
And (B) general formula (II)
R ⁴ —NR ² R ³ (II)
[Wherein, the substituent R ⁴ represents a linear or branched C ₆ -C ₆₀₀ alkyl group,
And R ² and R ^{3 as} substituents have the above meanings], and a method for producing an amine mixture containing 0.1 to 99.9 parts by mass of an aliphatic amine,
In this case, the sum of the parts by mass of the components (A) and (B) is 100 parts by mass, also in the above method,
The method is
(I) an oxo product formed during the hydroformylation of polybutene or polyisobutene and an alkanol of formula R ⁴ —OH or (ii) an epoxide generated during the epoxidation of polybutene or polyisobutene and an alkanol of formula R ⁴ —OH or (iii) ) A corresponding part by weight of a mixture of a nitro compound and an alkanol of the formula R ⁴ —OH formed during the reaction of polybutene or polyisobutene with nitrogen oxides or a mixture of nitrogen oxides and oxygen is converted to ammonia or the formula HNR ² R Characterized by reductive amination with ³ amines.

Since a part of the amine mixture described as a substance mixture is a novel substance-regardless of the form of production of the substance mixture-the subject of the present invention is
(A) General formula (I)
PIB (CH ₂ ) _x (OH) _m (NR ² R ³ ) _n (I)
[Where,
The PIB moiety represents a skeleton derived from polybutene or polyisobutene containing 0 to 20% by mass of n-butene or a polybutyl group or polyisobutyl group derived from isobutene and 0 to 20% by mass of n-butene,
The substituents R ² and R ³ may be the same or different, and may be hydrogen, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, a primary or secondary aromatic aminoalkylene group or an aliphatic amino group. An alkylene group or a primary or secondary aromatic polyaminoalkylene group or an aliphatic polyaminoalkylene group, a polyoxyalkylene group, a heteroaryl group or a heterocyclyl group, or a nitrogen atom to which they are bonded Together with a ring, there may still be heteroatoms in the ring, and the variable x can have a value of 0 or 1, and the variable m has a value of 0 or 1. And the variable n can take a value of 1, 2 or 3) 0.1-99.9 parts by weight of polyisobuteneamine
In that case, the polyisobutenamine (I) has a number average molecular weight of 300 to 2500,
And (B ′) general formula (II)
R ¹⁴ —NR ² R ³ (II)
[Wherein, the substituent R ¹⁴ represents a linear or branched C ₆ -C ₉ alkyl group,
And the substituents R ² and R ³ have the above meanings], containing 0.1 to 99.9 parts by weight of an aliphatic amine,
In this case, the total of the parts by mass of the components (A) and (B ′) is 100 parts by mass, which is also the amine mixture.
In particular, the amine mixture contains an aliphatic amine of the general formula (II) as component (B ′), wherein the substituent R ¹⁴ represents a branched C ₆ -C ₉ alkyl group, And the substituents R ² and R ³ each represent hydrogen.

Particularly preferably, the amine mixture contains an aliphatic amine of the general formula (II) as component (B ′), in which the substituent R ¹⁴ represents a 2-ethylhexyl group and Certain R ² and R ³ each represent hydrogen.

In particular, the amine mixture is used as component (A) in general formula (Ia)
R ¹ —CH ₂ —NR ² R ³ (Ia)
[In the formula, the substituent R ¹ represents a polybutyl group or a polyisobutyl group having a number average molecular weight of 300 to 2500 derived from 0 to 20% by mass of isobutene and n-butene, and the substituent R ² and R ³ represents each hydrogen], and as component (B ′), the substituent R ¹⁴ represents a 2-ethylhexyl group and the substituents R ² and R ³ likewise represent hydrogen, respectively. Contains an aliphatic amine of formula (II).

The amine mixture according to the invention consisting of the main components (A) and (B) or (A) and (B ′) is preferably used as a fuel additive, in particular in intake valves and direct injection in intake pipe injection Otto engines. Suitable for cleaning and maintaining clean injection nozzles in the Otto engine. Accordingly, fuel compositions, in particular Otto fuel compositions, containing the amine mixtures according to the invention are also the subject of the present invention. In particular, the fuel composition has an alcohol content, in particular a C ₁ -C ₄ alkanol, such as methanol or especially ethanol, in an amount of 0 to 100% by volume, particularly preferably more than 0 to 90% by volume, in particular 5 to 90%. It has a volume%, particularly 50 to 85 volume%, and is suitable for driving an Otto engine.

  Further, the object of the present invention is the main components (A) and (B) or (for cleaning and maintaining the intake valve in the intake pipe injection type Otto engine and the injection nozzle in the direct injection type Otto engine. The use of an amine mixture according to the invention consisting of A) and (B ′).

The amine mixture according to the present invention exhibits a very good detergent effect when driving an internal combustion engine using a fuel composition containing the amine mixture. In addition to the effect in cleaning and maintaining the entire intake valve, injection nozzle and intake system of the engine, the fuel composition also exhibits a series of further favorable effects as a fuel additive. The fuel composition reduces stickiness of the valve and / or the fuel composition is compatible with detergents and carrier oils, especially polyether carrier oils and polyetheramine carrier oils, especially at low temperatures. improve sex, and / or the fuel composition improves the compatibility of the fuel composition comprising a mineral fuel ratio and C ₁ -C ₄ alkanol. Furthermore, a fuel additive concentrate containing an amine mixture according to the present invention is sufficiently dilute (ie, the fuel additive concentrate exhibits a sufficiently low viscosity), and therefore the fuel additive concentrate. Insufficient capacity in manufacturing is avoided due to the time limited flow through the device and conduit--even when sharing inert solvents or diluents--relatively low viscosities are expected It also affects the mode of action as a fuel additive in an impossible and advantageous manner.

  A fuel composition is to be construed in particular in the context of the present invention as an Otto fuel composition. As the otto fuel, all commercially available otto fuel compositions fall under this category. Here, a typical representative example is the Eurosuper base fuel customary in the market as described in EN 228. Furthermore, a possible field of use for the amine mixtures according to the invention is also the standard otto fuel composition described in WO 00/47698.

  For example, mention may be made of an Otto fuel composition having an aromatic content of up to 60% by volume, for example up to 42% by volume and a sulfur content of up to 2000 ppm by weight, for example up to 150 ppm by weight.

  The aromatic compound content of the Otto fuel composition is in particular at most 50% by volume, in particular 1 to 45% by volume, in particular 5 to 40% by volume. The sulfur content of the Otto fuel is in particular at most 500 ppm by weight, in particular from 0.5 to 150 ppm by weight, in particular from 1 to 100 ppm by weight.

  Furthermore, the Otto fuel composition has, for example, an olefin content of up to 50% by volume, in particular 0.1 to 21% by volume, in particular 2 to 18% by volume, in particular up to 5% by volume, in particular 0 to 1.0% by volume, In particular, a benzene content of 0.05 to 0.9% by volume and / or an oxygen content of up to 47.5% by weight, for example 0.1 to 2.7% by weight or for example 2.7 to 47.5% by weight ( Otto fuel composition comprising mainly lower alcohols).

  In particular, at the same time an aromatic content of up to 38% by volume, an olefin content of up to 21% by volume, a sulfur content of up to 50 ppm by weight, a benzene content of up to 1.0% by volume and 0.1 to 47.5% by weight The Otto fuel composition having an oxygen content may be exemplified.

  The vapor pressure of the Otto fuel composition during the summer is usually up to 70 kPa, in particular 60 kPa (each at 37 ° C.).

  The ROZ of the Otto fuel composition is usually 75-105. The usual range for the corresponding MOZ is 65-95.

  The standard described is measured in the usual way (DIN EN 228).

  However, in addition to the use in Otto fuels, it is also possible in principle to use the amine mixtures according to the invention in other fuel types or power fuel types, for example diesel fuel, kerosene or turbine fuel. Use in a lubricant composition can also be envisaged.

Examples of C ₁ -C ₄ alkanols include methanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol and in particular ethanol, which are the C ₁ -C ₄ alkanols described. Mixtures can also be considered as lower alcohol fuel components. In addition to the lower alcohol fuel component described, the fuel composition according to the invention may further contain an ether having 5 or more carbon atoms in the molecule, for example methyl-t-butyl ether, in an amount of 30% by volume. it can.

  The amine mixture according to the invention can be added alone to the fuel composition to be added or can be added in a mixture with further active ingredients (co-additives).

As an example of this type of co-additive, an additive having a detergent effect and / or a valve seat wear resistance effect, which is different from component (A) of the amine mixture according to the invention (hereinafter referred to as detergent additive together) Can be used). The detergent additive is usually:
(A) a monoamino group or polyamino group having up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties;
(B) a nitro group, optionally in combination with a hydroxyl group,
(C) a hydroxyl group in combination with a monoamino group or a polyamino group, wherein at least one nitrogen atom has basic properties;
(D) a carboxyl group or an alkali metal salt or alkaline earth metal salt thereof,
(E) a sulfonic acid group or an alkali metal salt or alkaline earth metal salt thereof,
(F) end hydroxy group, or a monoamino group or polyamino groups, at least one nitrogen atom in that case, has the property of basic or polyoxy -C ₂ -C ₄ alkylene moiety having a carbamate group, ,
(G) a carboxylic acid ester group,
(H) a moiety derived from succinic anhydride having a hydroxy group and / or an amino group and / or an amide group and / or an imide group, and / or (i) by a Mannich reaction of a substituted phenol with an aldehyde and a monoamine or polyamine. Having at least one hydrophobic hydrocarbon group selected from the formed moieties, having a number average molecular weight ( _Mn ) of 85-20000 and at least one polar moiety.

Hydrophobic hydrocarbon groups in the detergent additive that ensure sufficient solubility in the fuel have a number average molecular weight ( _Mn ) of 85-20000, in particular 113-10000, in particular 300-5000. In particular, together with the polar parts (a), (c), (h) and (i), typical hydrophobic hydrocarbon groups of 300 to 5000, in particular 500 to 2500, in particular 700 to 2300 M _{n respectively.} This includes polypropenyl, polybutenyl and polyisobutenyl groups having

  Furthermore, the amine mixtures according to the invention can still be combined with the usual ingredients and additives. Here, for example, mention may be made of mineral-based carrier oils or synthetic-based carrier oils which do not have a significant detergent effect.

  Suitable mineral carrier oils are fractions produced during petroleum processing, such as kerosene or naphtha, bright stock or base oils having a viscosity from eg class SN 500-2000, but aromatic hydrocarbons, paraffins Also hydrocarbons and alkoxyalkanols. Similarly, the fraction known as “hydrocracked oil” and produced during the raffination of mineral oil (which can be obtained from natural mineral oil that has been catalytically hydrogenated, isomerized and deparaffinized under high pressure , A vacuum distillation cut having a boiling range of about 360-500 ° C) can also be used. Likewise suitable are mixtures of the above mineral carrier oils.

Examples of synthetic carrier oils that can be used are polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, polyethers starting with alkylphenols, It may be selected from alkylphenol-started polyetheramines and carboxylic acid esters of long-chain alkanols. Examples of particularly suitable synthetic carrier oils usually have about 5 to 35 C ₃ -C ₆ alkylene oxide units selected from propylene oxide units, n-butylene oxide units and isobutylene oxide units or mixtures thereof. An alcohol-started polyether. Non-limiting examples of suitable starting alcohols for this purpose are phenols substituted with long-chain alkanols or long-chain alkyls, in which long-chain alkyl groups are in particular straight-chain or branched chains. Represents a C ₆ -C ₁₈ alkyl group in the form of a ring. For this purpose, preferred examples include tridecanol and nonylphenol.

  Further conventional fuel additives are corrosion inhibitors based on, for example, ammonium salts of organic carboxylic acids, which have a tendency to form a film, or in the case of non-ferrous metal corrosion protection, for example Based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid. Antioxidants or stabilizers, demulsifiers (demulsifiers), antistatic agents, metallocenes such as ferrocene, methylcyclopentadienyl manganese tricarbonyl, lubricity improvers (lubricants), eg specific Fatty acids, alkenyl succinates, bis (hydroxyalkyls) Fatty amines, hydroxyacetamide or castor oil, as well as dyes (markers). Optionally, an amine that lowers the pH value of the fuel is also added.

  The components or additives described can be added individually to the fuel composition or can be added together with the amine mixture according to the invention as a previously prepared concentrate (package additive).

  The amine mixture according to the invention is usually added to the fuel composition-separately or in the form of concentrates with other components or additives and optionally conventional solvents and diluents-usually in the total amount of the fuel composition. On the other hand, each is defined as a pure substance content (ie without solvents and diluents and other components or additives) 5 to 5000 ppm by weight, in particular 10 to 2000 ppm by weight, in particular 25 to 1000 ppm by weight, in particular It is added in an amount of 50 to 500 ppm by mass. Other listed ingredients or additives are added in conventional amounts for this purpose, if desired.

  The present invention will be described with reference to the following examples, but is not limited thereto.

EXAMPLE 500 g of polyisobutene having a number average molecular weight of 1000 and a proportion of vinylidene double bonds greater than 70%, 200 g of a solvent mixture consisting of 80% by weight of Mihagor® M and 20% by weight of Nesol LIAV® 230 and cobalt 2.8 g of the carbonyl catalyst were heated at 280 bar carbon monoxide / hydrogen with stirring in a 2.5 liter reciprocating autoclave for 5 hours at 185 ° C. Thereafter, the mixture was cooled to room temperature, the catalyst was removed with 400 ml of 10% by weight acetic acid and the mixture was washed until neutral. The resulting oxo product was treated with 180 g of 2-ethylhexanol, 1.0 liter of ammonia and 100 g of Raney cobalt catalyst in a 5 liter roll autoclave at 180 ° C. under 200 bar hydrogen pressure. After cooling the mixture, the Raney cobalt catalyst was filtered off, excess ammonia was evaporated and the solvent was distilled off.

Claims (13)

As the main ingredient,
(A) General formula (I)
PIB (CH ₂ ) _x (OH) _m (NR ² R ³ ) _n (I)
[Where,
The PIB moiety represents a skeleton derived from polybutene or polyisobutene containing 0 to 20% by mass of n-butene or a polybutyl group or polyisobutyl group derived from isobutene and 0 to 20% by mass of n-butene,
The substituents R ² and R ³ may be the same or different, and may be hydrogen, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, a primary or secondary aromatic aminoalkylene group or an aliphatic amino group. An alkylene group or a primary or secondary aromatic polyaminoalkylene group or an aliphatic polyaminoalkylene group, a polyoxyalkylene group, a heteroaryl group or a heterocyclyl group, or a nitrogen atom to which they are bonded Together with a ring, there may still be heteroatoms in the ring, and the variable x can have a value of 0 or 1, and the variable m has a value of 0 or 1. And the variable n can take a value of 1, 2 or 3) 0.1-99.9 parts by weight of polyisobuteneamine
In that case, the polyisobutenamine (I) has a number average molecular weight of 300 to 2500,
And (B) general formula (II)
R ⁴ —NR ² R ³ (II)
[Wherein, the substituent R ⁴ represents a linear or branched C ₆ -C ₆₀₀ alkyl group,
And R ² and R ^{3 as} substituents have the above meanings], and an amine mixture containing 0.1 to 99.9 parts by mass of an aliphatic amine.
In that case, the sum total of the mass parts of the components (A) and (B) is 100 parts by mass,
(I) an oxo product formed during the hydroformylation of polybutene or polyisobutene and an alkanol of formula R ⁴ —OH or (ii) an epoxide generated during the epoxidation of polybutene or polyisobutene and an alkanol of formula R ⁴ —OH or (iii) ) A corresponding part by weight of a mixture of a nitro compound and an alkanol of the formula R ⁴ —OH formed during the reaction of polybutene or polyisobutene with nitrogen oxides or a mixture of nitrogen oxides and oxygen is converted to ammonia or the formula HNR ² R Said amine mixture obtained by reductive amination with an amine of ³ . As the main ingredient,
(A) General formula (Ia)
R ¹ —CH ₂ —NR ² R ³ (Ia)
[Wherein, the substituent R ¹ represents a polybutyl group or a polyisobutyl group derived from 0 to 20% by mass of isobutene and n-butene, and the substituents R ² and R ³ have the above-mentioned meanings] 0.1-99.9 parts by weight of polyisobuteneamine,
And (B) 0.1 to 99.9 parts by mass of the aliphatic amine of the general formula (II),
By reductive amination of a corresponding part by weight of an oxo product and an alkanol of the formula R ⁴ —OH, produced during the hydroformylation of polybutene or polyisobutene, with ammonia or an amine of the formula HNR ² R ³ The amine mixture of claim 1 obtained.   The amine mixture according to claim 1 or 2, comprising as component (A) a polyisobuteneamine of formula (I) or (Ia) having an average molecular weight of 500 to 1500. Component (B) is represented by the formula R ⁴ —NH _{2 wherein} the substituent R ⁴ is a linear or branched C ₇ -C ₂₃ alkyl group or a polybutyl group having 24 to 600 carbon atoms. Or an amine mixture according to any one of claims 1 to 3, which contains an aliphatic amine.   50 to 95 parts by weight of component (A), in particular 70 to 90 parts by weight and 5 to 50 parts by weight, in particular 10 to 30 parts by weight of component (B), in which components (A) and (B 5) The amine mixture according to any one of claims 1 to 4, wherein the sum of the parts by mass is 100 parts by mass. As the main ingredient,
(A) General formula (I)
PIB (CH ₂ ) _x (OH) _m (NR ² R ³ ) _n (I)
[Where,
The PIB moiety represents a skeleton derived from polybutene or polyisobutene containing 0 to 20% by mass of n-butene or a polybutyl group or polyisobutyl group derived from isobutene and 0 to 20% by mass of n-butene,
The substituents R ² and R ³ may be the same or different, and may be hydrogen, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, a primary or secondary aromatic aminoalkylene group or an aliphatic amino group. An alkylene group or a primary or secondary aromatic polyaminoalkylene group or an aliphatic polyaminoalkylene group, a polyoxyalkylene group, a heteroaryl group or a heterocyclyl group, or a nitrogen atom to which they are bonded Together with a ring, there may still be heteroatoms in the ring, and the variable x can have a value of 0 or 1, and the variable m has a value of 0 or 1. And the variable n can take a value of 1, 2 or 3) 0.1-99.9 parts by weight of polyisobuteneamine
In that case, the polyisobutenamine (I) has a number average molecular weight of 300 to 2500,
And (B) general formula (II)
R ⁴ —NR ² R ³ (II)
[Wherein, the substituent R ⁴ represents a linear or branched C ₆ -C ₆₀₀ alkyl group,
And R ² and R ^{3 as} substituents have the above meanings], and a method for producing an amine mixture containing 0.1 to 99.9 parts by mass of an aliphatic amine,
In that case, the sum of the parts by mass of the components (A) and (B) is 100 parts by mass,
(I) an oxo product formed during the hydroformylation of polybutene or polyisobutene and an alkanol of formula R ⁴ —OH or (ii) an epoxide generated during the epoxidation of polybutene or polyisobutene and an alkanol of formula R ⁴ —OH or (iii) ) A corresponding part by weight of a mixture of a nitro compound and an alkanol of the formula R ⁴ —OH formed during the reaction of polybutene or polyisobutene with nitrogen oxides or a mixture of nitrogen oxides and oxygen is converted to ammonia or the formula HNR ² R Said process characterized by reductive amination with an amine of ³ . As the main ingredient,
(A) General formula (I)
PIB (CH ₂ ) _x (OH) _m (NR ² R ³ ) _n (I)
[Where,
The PIB moiety represents a skeleton derived from polybutene or polyisobutene containing 0 to 20% by mass of n-butene or a polybutyl group or polyisobutyl group derived from isobutene and 0 to 20% by mass of n-butene,
The substituents R ² and R ³ may be the same or different, and may be hydrogen, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, a primary or secondary aromatic aminoalkylene group or an aliphatic amino group. An alkylene group or a primary or secondary aromatic polyaminoalkylene group or an aliphatic polyaminoalkylene group, a polyoxyalkylene group, a heteroaryl group or a heterocyclyl group, or a nitrogen atom to which they are bonded Together with a ring, there may still be heteroatoms in the ring, and the variable x can have a value of 0 or 1, and the variable m has a value of 0 or 1. And the variable n can take a value of 1, 2 or 3) 0.1-99.9 parts by weight of polyisobuteneamine
In that case, the polyisobutenamine (I) has a number average molecular weight of 300 to 2500,
And (B ′) general formula (II)
R ¹⁴ —NR ² R ³ (II)
[Wherein, the substituent R ¹⁴ represents a linear or branched C ₆ -C ₉ alkyl group,
And R ² and R ^{3 as} substituents have the above meanings] 0.1-99.9 parts by weight of an aliphatic amine
In that case, the sum total of the mass part of a component (A) and (B ') is an amine mixture which is 100 mass parts. The component (B ′) is a fatty acid of the general formula (II) in which the substituent R ¹⁴ represents a branched C ₆ -C ₉ alkyl group, and the substituents R ² and R ³ each represent a hydrogen atom. 8. The amine mixture according to claim 7, which contains a group amine. The component (B ′) contains an aliphatic amine of the general formula (II) in which the substituent R ¹⁴ represents a 2-ethylhexyl group and the substituents R ² and R ³ each represent a hydrogen atom. 9. The amine mixture according to 8. As the component (A), the general formula (Ia)
R ¹ —CH ₂ —NR ² R ³ (Ia)
[In the formula, the substituent R ¹ represents a polybutyl group or a polyisobutyl group having a number average molecular weight of 300 to 2500 derived from 0 to 20% by mass of isobutene and n-butene, and the substituent R ² and R ³ is a polyisobutene amine and components of each represent hydrogen] (B '), the general formula R ² and R ³ substituents R ¹⁴ is represented and a substituent of 2-ethylhexyl hydrogen respectively in the same manner 10. The amine mixture according to claim 9, containing an aliphatic amine of (II).   A fuel composition comprising the amine mixture according to any one of claims 1 to 10.   12. The fuel composition according to claim 11, which has an alcohol content of 0 to 100% by volume and is suitable for driving an Otto engine.   Use of an amine mixture according to any one of claims 1 to 10 to clean and keep the intake valves in an in-pipe injection Otto engine and the injection nozzles in a direct injection Otto engine.