EP3609986B1 - Alkoxylated amines as fuel additive - Google Patents

Description

The present invention describes alkoxylated amines as fuel additives to reduce injector deposits in direct injection gasoline engines.

Out of EP 700985 A1 is known to use butoxylated polyetheramines of mono- or polyamines as additives in fuels for gasoline engines. The polyetheramines show a reduction in deposits on the intake valves. The polyetheramines are prepared by butoxylation of alkanols, followed by reductive amination of the products obtained with mono- or polyamines. The polyetheramines therefore do not carry any free hydroxyl groups, but instead carry alkyl-capped butylene oxide chains.

Out of WO 2011/076949 discloses the use of mixed ethoxylated/propoxylated polyetheramines of monoamines in alcohol-containing gasoline to improve fuel economy and/or reduce deposits on intake valves and/or injection nozzles.

Out of DE 10316871 A1 and EP 310875 A1 it is known to use polyetheramines such as tridecanol or isotridecanol propoxylate and/or butoxylate ammonia reaction products in fuels.

DC Arters et al., SAE Tech Paper Ser 2000, International Spring Fuels & Lubricants Meeting & Exposition, Paris, France, June 19-22, 2000 generically describe the use of polyisobuteneamine-containing compositions and unspecified polyetheramine in various fuels and applications without characterizing the components used.

EP 905217 A describes the use of ether group-containing compounds in gasoline for direct-injection gasoline engines to reduce emissions. To further reduce injector deposits or combustion chamber deposits, polyalkylamines or polyetheramines should be added to the fuel.

The object of the present invention was to provide compounds with which the formation of deposits on injection nozzles can be avoided or reduced and/or existing deposits can be removed in direct-injection Otto engines.

und Formel (II)

worin

• R einen zweibindigen organischen Rest, bevorzugt einen 2 bis 10 Kohlenstoffatome aufweisenden Alkylenrest,
• R¹, R², R³, R⁴, R⁵ und R⁶ unabhängig voneinander Wasserstoff oder einen einbindigen organischen Rest oder einen Rest -[-X_i-]_n-H oder R¹ und R² gemeinsam und zusammen mit dem Stickstoffatom einen fünf- bis siebengliedrigen Ring bilden können, bevorzugt Wasserstoff, einen 1 bis 20 Kohlenstoffatome aufweisenden Alkylrest oder einen Rest -[-X_i-]_n-H,
• w eine positive ganze Zahl und
• x, y und z unabhängig voneinander Null oder eine positive ganze Zahl

bedeuten,

• worin n eine positive ganze Zahl bedeutet, und
• worin jedes X_i für i = 1 bis n unabhängig voneinander ausgewählt ist aus der Gruppe bestehend aus -CH₂-CH₂-O-, -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -C H₂-CH(C₂H₅)-O-, -CH(C₂H₅)-CH₂-O- und -CH(CH₃)-CH(CH₃)-O-, bevorzugt ausgewählt aus der Gruppe bestehend aus -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -CH₂-CH(C₂H₅)-O -, -CH(C₂H₅)-CH₂-O- und -CH(CH₃)-CH(CH₃)-O-, besonders bevorzugt ausgewählt aus der Gruppe bestehend aus -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -CH₂-CH(C₂H₅)-O
• und -CH(C₂H₅)-CH₂-O-, ganz besonders bevorzugt ausgewählt aus der Gruppe bestehend aus -CH₂-CH(C₂H₅)-O-, -CH(C₂H₅)-CH₂-O-, -CH₂-CH(CH₃)-O- und -CH(CH₃)-CH₂-O-, und insbesondere ausgewählt aus der Gruppe bestehend aus -CH₂-CH(CH₃)-O- und -CH(CH₃)-CH₂-O-, mit der Maßgabe, daß
• die Summe aus x, y und z ungleich Null ist
• mindestens einer der Reste R¹, R², R³, R⁴, R⁵ und R⁶ nicht Wasserstoff ist und
• mindestens einer der Reste R¹, R², R³, R⁴, R⁵ und R⁶ einen Rest -[-X_i-]_n-H darstellt,

in Ottokraftstoffen zur Vermeidung und/oder Verringerung der Bildung von Ablagerungen an Einspritzdüsen in direkteinspritzenden Ottomotoren und/oder Entfernung und/oder Verringerung von bestehenden Ablagerungen an Einspritzdüsen in direkteinspritzenden Ottomotoren.The object was achieved by using compounds (A) selected from the group consisting of

and formula (II)

wherein

• R is a divalent organic radical, preferably an alkylene radical having 2 to 10 carbon atoms,
• R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently hydrogen or a monovalent organic radical or a radical -[-X _i -] _n -H or R ¹ and R ² together and together with the nitrogen atom can form a five- to seven-membered ring, preferably hydrogen, an alkyl radical having 1 to 20 carbon atoms or a radical -[-X _i -] _n -H,
• w a positive integer and
• x, y, and z are independently zero or a positive integer

mean,

• where n is a positive integer, and
• wherein each X _i for i = 1 to n is independently selected from the group consisting of -CH ₂ -CH ₂ -O-, -CH ₂ -CH(CH ₃ )-O-, -CH(CH ₃ )-CH ₂ -O-, -CH ₂ -C(CH ₃ ) ₂ -O-, -C(CH ₃ ) ₂ -CH ₂ -O-, -CH ₂ -CH(C ₂ H ₅ )-O-, -CH (C ₂ H ₅ )-CH ₂ -O- and -CH(CH ₃ )-CH(CH ₃ )-O-, preferably selected from the group consisting of -CH ₂ -CH(CH ₃ )-O-, - CH(CH ₃ )-CH ₂ -O-, -CH ₂ -C(CH ₃ ) ₂ -O-, -C(CH ₃ ) ₂ -CH ₂ -O-, -CH ₂ -CH(C ₂ H ₅ )-O-, -CH(C ₂ H ₅ )-CH ₂ -O- and -CH(CH ₃ )-CH(CH ₃ )-O-, particularly preferably selected from the group consisting of -CH ₂ -CH( CH3 )-O-, -CH(CH3 ) _-CH2 -O-, _-CH2 -C(CH3 _{)2 -O-} , -C _{( CH3 )2 -CH2 -O-} , -CH ₂ -CH(C ₂ H ₅ )-O
• and -CH(C ₂ H ₅ )-CH ₂ -O-, most preferably selected from the group consisting of -CH ₂ -CH(C ₂ H ₅ )-O-, -CH(C ₂ H ₅ )-CH ₂ -O-, -CH ₂ -CH(CH ₃ )-O- and -CH(CH ₃ )-CH ₂ -O-, and in particular selected from the group consisting of -CH ₂ -CH(CH ₃ )-O- - and -CH(CH ₃ )-CH ₂ -O-, with the proviso that
• the sum of x, y, and z is non-zero
• at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is not hydrogen and
• at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represents a radical -[-X _i -] _n -H,

in petrol to prevent and/or reduce the formation of deposits on injector nozzles in direct-injection petrol engines and/or remove and/or reduce existing deposits on injector nozzles in direct-injection petrol engines.

Among these, the compounds of formula (I) are preferred.

worin

• R¹, R² und X_i die oben genannten Bedeutungen haben und
• p und q unabhängig voneinander eine positive ganze Zahl bedeuten.

In a preferred embodiment, the compounds have the formula (III)

wherein

• R ¹ , R ² and X _i have the meanings given above and
• p and q independently represent a positive integer.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently hydrogen or a monovalent organic radical or R ¹ and R ² together and together with the nitrogen atom can form a five- to seven-membered ring.

Preferred monovalent organic radicals are C ₁ - to C ₂₀ -alkyl, C ₅ - to C ₁₂ -cycloalkyl, C ₆ - to C ₁₂ -aryl or a radical -[-X _i -] _n -H, particularly preferably C ₁ - to C ₁₀ -alkyl, C ₅ - to C ₆ -cycloalkyl, C ₆ - to C ₁₂ -aryl or a radical -[-X _i -] _n -H, very particularly preferably particularly preferably C ₁ - to C ₄ -alkyl , especially methyl.

R ¹ and R ² are preferably both the same and are each C ₁ - to C ₄ -alkyl and particularly preferably methyl.

Furthermore, it is possible for R ¹ and R ² together and together with the nitrogen atom to form a five- to seven-membered ring, particularly a five- or six-membered ring and particularly preferably a six-membered ring.

The proviso applies that at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is not hydrogen and at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a radical -[-X _i -] _n -H, preferably at least two of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are a radical -[-X _i -] _n -H .

R is a divalent organic radical, preferably an alkylene radical having 2 to 10 carbon atoms, preferably an alkylene radical having 2 to 6 carbon atoms, particularly preferably an alkylene radical having 2 to 4 carbon atoms, very particularly preferably an alkylene radical having 2 or 3 carbon atoms and in particular an alkylene radical having 3 carbon atoms having alkylene radical.

Preferably R is 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene , 1,8-octylene or 1,10-decylene, particularly preferably 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene or 1,6-hexylene , very particularly preferably 1,2-ethylene, 1,2-propylene or 1,3-propylene and for compounds of the formula (I) or (III) in particular 1,3-propylene and for compounds of the formula (II) in particular 1, 2-ethylene or 1,3-propylene, especially 1,2-ethylene.

Furthermore, w is a positive integer, preferably 1, 2, 3 or 4, particularly preferably 1, 2 or 3, very particularly preferably 1 or 2 and in particular 1.

Furthermore, x, y and z, independently of one another, are positive integers, preferably 1, 2, 3 or 4, particularly preferably 1, 2 or 3, very particularly preferably 1 or 2 and in particular 1.

The proviso applies that the sum of x, y and z is not equal to zero, preferably the sum of x, y and z is at least 2, particularly preferably at least 3.

The sum of x, y and z is preferably not greater than 10, particularly preferably not greater than 8, very particularly preferably not greater than 6 and in particular not greater than 5.

Further, each X _i for i = 1 through n is independently selected from the group consisting of -CH ₂ -CH ₂ -O-, -CH ₂ -CH(CH ₃ )-O-, -CH(CH ₃ )- CH ₂ -O-, -CH ₂ -C(CH ₃ ) ₂ -O-, -C(CH ₃ ) ₂ -CH ₂ -O-, -CH ₂ -CH(C ₂ H ₅ )-O-, - CH(C ₂ H ₅ )-CH ₂ -O- and -CH(CH ₃ )-CH(CH ₃ )-O-, preferably selected from the group consisting of -CH ₂ -CH(CH ₃ )-O-, -CH(CH ₃ )-CH ₂ -O-, -CH ₂ -C(CH ₃ ) ₂ -O-, -C(CH ₃ ) ₂ -CH ₂ -O-, -CH ₂ -CH(C ₂ H ₅ )-O-, -CH(C ₂ H ₅ )-CH ₂ -O- and -CH(CH ₃ )-CH(CH ₃ )-O-, particularly preferably selected from the group consisting of -CH ₂ -CH (CH ₃ )-O-, -CH(CH ₃ )-CH ₂ -O-, -CH ₂ -C(CH ₃ ) ₂ -O-, -C(CH ₃ ) ₂ -CH ₂ -O-, - CH ₂ -CH(C ₂ H ₅ )-O- and -CH(C ₂ H ₅ )-CH ₂ -O- and most preferably selected from the group consisting of -CH ₂ -CH(C ₂ H ₅ )- O-, -CH(C ₂ H ₅ )-CH ₂ -O-, -CH ₂ -CH(CH ₃ )-O- and -CH(CH ₃ )-CH ₂ -O-, and in particular selected from the group consisting of -CH ₂ -CH(CH ₃ )-O- and -CH(CH ₃ )-CH ₂ -O-.

It should be noted that in each chain -[-X _i -] _n - occurring in the compounds, the units X _i can be statistically distributed, so that both the length of the chains and the distribution of the units X _i within the chains are different can be.

Furthermore, n, p and q independently of one another are positive integers from 1 to 50, preferably from 1 to 25, particularly preferably from 2 to 20 and very particularly preferably from 5 to 15.

The sum of p and q is preferably from 2 to 50, particularly preferably from 5 to 40, very particularly preferably from 10 to 30 and in particular from 12 to 27.

Examples of C ₁ - to C ₂₀ -alkyl are methyl, ethyl, isopropyl , n-propyl, n-butyl, isobutyl , sec -butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl , 2-ethylhexyl, n-decyl, 2-propylheptyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.

Examples of C ₁ - to C ₁₀ -alkyl are methyl, ethyl, isopropyl , n-propyl, n-butyl, isobutyl , sec- butyl, tert -butyl , n-hexyl, n-heptyl, n-octyl , 2-ethylhexyl, n-decyl and 2-propylheptyl.

Examples of C ₁ - to C ₄ -alkyl are methyl, ethyl, isopropyl , n-propyl, n-butyl, isobutyl , sec- butyl and tert -butyl , preferably methyl, ethyl and n-butyl, particularly preferred methyl and ethyl and most preferably methyl.

Examples of C ₅ - to C ₁₂ -cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl, preference being given to cyclopentyl and cyclohexyl.

Examples of C ₆ to C ₁₂ aryl are phenyl, tolyl, ethylphenyl, benzyl, phenethyl, xylyl and naphthyl.

• (la) R sei 1,2-Ethylen, w = 1, R¹ bis R³ Methyl und R⁴ eine Kette -[-X_i-]_n-H.
• (Ib) R sei 1,2-Ethylen, w = 1, R¹ und R² Methyl und R³ und R⁴ jeweils unabhängig voneinander eine Kette -[-X_i-]_n-H.
• (Ic) R sei 1,2-Propylen, w = 1, R¹ und R² Methyl und R³ und R⁴ jeweils unabhängig voneinander eine Kette -[-X_i-]_n-H.
• (Id) R sei 1,3-Propylen, w = 1, R¹ und R² Methyl und R³ und R⁴ jeweils unabhängig voneinander eine Kette -[-X_i-]_n-H.
• (Ie) R sei 1,3-Propylen, w = 1, R¹ und R² Ethyl und R³ und R⁴ jeweils unabhängig voneinander eine Kette -[-X_i-]_n-H.
• (If) R sei 1,3-Propylen, w = 1, R¹ und R² n-Butyl und R³ und R⁴ jeweils unabhängig voneinander eine Kette -[-X_i-]_n-H.
• (Ig) R sei 1,2-Ethylen, w = 1, R¹ bis R⁴ eine Kette -[-X_i-]_n-H.

The following compounds of the formula (I) represent preferred embodiments:

• (la) R is 1,2-ethylene, w=1, R ¹ to R ³ are methyl and R ⁴ is a chain -[-X _i -] _n -H.
• (Ib) R is ^1,2 -ethylene, w= ¹ , R1 and R2 are methyl and ^R3 and ^R4 are each independently a chain -[-X _i -] _n -H.
• (Ic) R is 1,2-propylene, w=1, R ¹ and R ² are methyl and R ³ and R ⁴ are each independently a chain -[-X _i -] _n -H.
• (Id) R is 1,3-propylene, w=1, R ¹ and R ² are methyl and R ³ and R ⁴ are each independently a chain -[-X _i -] _n -H.
• (Ie) R is 1,3-propylene, w=1, R ¹ and R ² are ethyl and R ³ and R ⁴ are each independently a chain -[-X _i -] _n -H.
• (If) R is 1,3-propylene, w=1, R ¹ and R ² are n-butyl and R ³ and R ⁴ are each independently a chain -[-X _i -] _n -H.
• (Ig) R is 1,2-ethylene, w=1, R ¹ to R ^{4 are} a chain -[-X _i -] _n -H.

Among these, compounds (Id) are particularly preferred.

• (IIa) R sei 1,2-Ethylen, x und y 1, z = 0 und R¹ bis R⁴ und R⁶ jeweils unabhängig voneinander eine Kette -[-X_i-]_n-H.
• (IIb) R sei 1,2-Propylen, x und y 1, z = 0 und R¹ bis R⁴ und R⁶ jeweils unabhängig voneinander eine Kette -[-X_i-]_n-H.
• (IIc) R sei 1,3-Propylen, x und y 1, z = 0 und R¹ bis R⁴ jeweils unabhängig voneinander eine Kette -[-X_i-]_n-H und R⁶ C₁- bis C₂₀-Alkyl.

The following compounds of the formula (II) are preferred:

• (IIa) R is 1,2-ethylene, x and y are 1, z=0 and R ¹ to R ⁴ and R ⁶ are each independently a chain -[-X _i -] _n -H.
• (IIb) R is 1,2-propylene, x and y are 1, z=0 and R ¹ to R ⁴ and R ⁶ are each independently a chain -[-X _i -] _n -H.
• (IIc) R is 1,3-propylene, x and y are 1, z = 0 and R ¹ to R ⁴ are each independently a chain -[-X _i -] _n -H and R ⁶ is C ₁ - to C ₂₀ - alkyl.

Among these, compounds (IIa) are particularly preferred.

(IIIa)

R sei 1,2-Ethylen und R¹ und R² Methyl

(IIIb)

R sei 1,2-Ethylen und R¹ und R² Ethyl

(IIIc)

R sei 1,2-Ethylen und R¹ und R² n-Butyl

(IIId)

R sei 1,2-Ethylen und R¹ und R² gemeinsam eine 1,4-Butylenkette

(IIIe)

R sei 1,2-Ethylen und R¹ und R² gemeinsam eine 1,5-Pentylenkette

(IIIf)

R sei 1,2-Ethylen und R¹ und R² gemeinsam eine 3-Oxa-1,5-pentylenkette

(IIIg)

R sei 1,2-Propylen und R¹ und R² Methyl

(IIIh)

R sei 1,2-Propylen und R¹ und R² Ethyl

(IIIi)

R sei 1,2-Propylen und R¹ und R² n-Butyl

(IIIj)

R sei 1,2-Propylen und R¹ und R² gemeinsam eine 1,4-Butylenkette

(IIIk)

R sei 1,2-Propylen und R¹ und R² gemeinsam eine 1,5-Pentylenkette

(IIII)

R sei 1,2-Propylen und R¹ und R² gemeinsam eine 3-Oxa-1,5-pentylenkette

(IIIm)

R sei 1,3-Propylen und R¹ und R² Methyl

(IIIn)

R sei 1,3-Propylen und R¹ und R² Ethyl

(IIIo)

R sei 1,3-Propylen und R¹ und R² n-Butyl

(IIIp)

R sei 1,3-Propylen und R¹ und R² gemeinsam eine 1,4-Butylenkette

(IIIq)

R sei 1,3-Propylen und R¹ und R² gemeinsam eine 1,5-Pentylenkette

(IIIr)

R sei 1,3-Propylen und R¹ und R² gemeinsam eine 3-Oxa-1,5-pentylenkette

The following compounds of the formula (III) are preferred:

(IIIa)

R is 1,2-ethylene and R ¹ and R ² are methyl

(IIIb)

R is 1,2-ethylene and R ¹ and R ² are ethyl

(IIIc)

R is 1,2-ethylene and R ¹ and R ² are n-butyl

(IIId)

R is 1,2-ethylene and R ¹ and R ² together are a 1,4-butylene chain

(IIIe)

R is 1,2-ethylene and R ¹ and R ² together are a 1,5-pentylene chain

(IIIf)

R is 1,2-ethylene and R ¹ and R ² together are a 3-oxa-1,5-pentylene chain

(IIIg)

R is 1,2-propylene and R ¹ and R ² are methyl

(IIIh)

R is 1,2-propylene and R ¹ and R ² are ethyl

(IIIi)

R is 1,2-propylene and R ¹ and R ² are n-butyl

(IIIj)

R is 1,2-propylene and R ¹ and R ² together are a 1,4-butylene chain

(IIIk)

R is 1,2-propylene and R ¹ and R ² together are a 1,5-pentylene chain

(III)

R is 1,2-propylene and R ¹ and R ² together are a 3-oxa-1,5-pentylene chain

(IIIm)

R is 1,3-propylene and R ¹ and R ² are methyl

(IIIn)

R is 1,3-propylene and R ¹ and R ² are ethyl

(IIIo)

R is 1,3-propylene and R ¹ and R ² are n-butyl

(IIIp)

R is 1,3-propylene and R ¹ and R ² together are a 1,4-butylene chain

(IIIq)

R is 1,3-propylene and R ¹ and R ² together are a 1,5-pentylene chain

(IIIr)

R is 1,3-propylene and R ¹ and R ² together are a 3-oxa-1,5-pentylene chain

Among these, compounds (IIIg) are particularly preferred.

The reaction products of 1,2-ethylenediamine, diethylenetriamine, triethylenetetramine or 3-(dimethylamino)propylamine, preferably diethylenetriamine or 3-(dimethylamino)propylamine and particularly preferably 3-(dimethylamino)propylamine with 10 to 30, preferably 12 to 27, are particularly preferred and more preferably 15 to 25 equivalents of propylene oxide and/or 1,2-butylene oxide.

The compounds described are used according to the invention in order to avoid or reduce the formation of deposits on direct-injection injection nozzles and/or to remove or reduce existing deposits when operating direct-injection Otto engines with Otto fuels.

It is an advantage of the described compounds that they can act as an alternative or in addition to this described use as a carrier oil, so that one can reduce the amount of carrier oil in the additive packages (see below).

Another advantage of the compounds described is that they can act as demulsifiers as an alternative or in addition to the uses described.

Another object of the present invention are fuel additive concentrates according to claim 14.

The production of alkoxylated amines (amines with primary and/or secondary amino groups) is known in principle, for example it is HL Sanders et al., Journal of the American Oil Chemists Society, 1969, 46, 167-170 and in WO 2013/076024 described.

The alkoxylation of amines and polyamines usually takes place in two stages: first, enough alkylene oxide is used to achieve an average degree of alkoxylation of from 0.5 to 1.5, preferably from 0.75 to 1.25, mol of alkylene oxide per NH function. This step is usually carried out in the presence of water (preferably 0.5-10.0% by weight based on the amine used), but can also be carried out in the absence of water. The reaction usually takes place at a temperature of from 50.degree. C. to 180.degree. C., preferably from 90.degree. C. to 160.degree. The alkylene oxide is preferably metered in over a period of 1 to 10 hours.

The further build-up of polyalkylene oxide chains takes place under base catalysis after removal of the solvent, in particular water. Examples of basic catalysts used are: Potassium hydroxide, sodium hydroxide, potassium methoxide or sodium methoxide, preferably potassium hydroxide or sodium hydroxide.

However, the synthesis of the alkoxylated amines can also take place in one stage, with potassium hydroxide, sodium hydroxide, potassium methoxide, sodium methoxide, potassium acetate or sodium acetate being able to be used as possible catalysts.

In principle, however, the reaction can also take place without a catalyst, since the amine used can itself catalyze the alkoxylation (see Mihail Ionescu, Chemistry and Technology of Polyols for Polyurethanes, Rapra Technology Limited, 2005).

The alkylene oxides usually contain 2 or more carbon atoms, preferably 2 to 20 carbon atoms, in particular from 2 to 12 carbon atoms. Possible alkylene oxides are ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, 1,2-dodecene oxide, styrene oxide. Possible alkylene oxides also include glycidyl ethers, for example 2-ethylhexyl glycidyl ether. Propylene oxide and 1,2-butylene oxide are particularly preferred.

If a metal-containing catalyst has been used, the metal is advantageously removed from the product for use in fuels or lubricants. These methods are known in principle and are described in Mihail Ionescu, Chemistry and Technology of Polyols for Polyurethanes, Rapra Technology Limited, 2005. Thus, alkali metals or alkaline earth metals can be removed by adsorption on magnesium silicates (commercial products ^Ambosol® or ^Magnesol® ). Potassium ions can be removed as potassium hydrogen phosphate by precipitation with phosphoric acid and subsequent filtration. Alkali metals or alkaline earth metals can also be removed with the aid of regenerable ion exchangers, in which case the alkoxylated amine can also be dissolved in a solvent.

B) Other additive components

The compounds (A) according to the invention can be added to the fuels to which additives are to be added individually or as a mixture with other active additive components (co-additives).

B1) Detergent additives

1. (a) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
2. (b) Nitrogruppen, ggf. in Kombination mit Hydroxylgruppen;
3. (c) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
4. (d) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
5. (e) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
6. (f) Polyoxy-C₂- bis C₄-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;
7. (g) Carbonsäureestergruppen;
8. (h) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder
9. (i) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugten Gruppierungen;

Additives with a detergent effect and/or with a valve seat wear-inhibiting effect (hereinafter referred to as detergent additives) can be mentioned as examples. This detergent additive has at least one hydrophobic hydrocarbon radical with a number average molecular weight (Mn) of 85 to 20,000 and at least one polar moiety selected from:

1. (a) mono- or polyamino groups containing up to 6 nitrogen atoms, where at least one nitrogen atom has basic properties;
2. (b) nitro groups, optionally in combination with hydroxyl groups;
3. (c) hydroxyl groups in combination with mono- or polyamino groups, where at least one nitrogen atom has basic properties;
4. (d) carboxyl groups or their alkali metal or alkaline earth metal salts;
5. (e) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
6. (f) polyoxy-C ₂ - to C ₄ -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, where at least one nitrogen atom has basic properties, or by carbamate groups;
7. (g) carboxylic acid ester groups;
8. (h) moieties derived from succinic anhydride having hydroxy and/or amino and/or amido and/or imido groups; and or
9. (i) moieties generated by Mannich reactions of substituted phenols with aldehydes and mono- or polyamines;

The hydrophobic hydrocarbon group in the above detergent additives which provides sufficient solubility in fuel has a number average molecular weight (Mn) of from 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5000. As a typical hydrophobic hydrocarbon group, especially in combination with the polar groups (a), (c), (h) and (i), the polypropenyl, polybutenyl and polyisobutenyl radicals, each with Mn=300 to 5000, in particular 500 to 2500, especially 700 to 2300, are suitable .

The following may be mentioned as examples of the above groups of detergent additives:
Additives containing mono- or polyamino groups (a) are preferably polyalkenemono- or polyalkenepolyamines based on polypropene or conventional (ie with predominantly central double bonds) polybutene or polyisobutene with Mn=300 to 5000. If polybutene or polyisobutene is included in the preparation of the additives predominantly central double bonds (usually in the beta and gamma position), the production route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to form the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions is an option. Amines such as ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be used for the amination. Corresponding additives based on polypropylene are in particular in the WO-A-94/24231 described.

Other preferred additives containing monoamino groups (a) are the hydrogenation products of the reaction products of polyisobutenes with an average degree of polymerization P=5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as they are used in particular in WO-A-97/03946 are described.

Other preferred additives containing monoamino groups (a) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as they are used in particular in DE-A-196 20 262 are described.

Additives containing nitro groups (b), optionally in combination with hydroxyl groups, are preferably reaction products of polyisobutenes with an average degree of polymerization P=5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as are found in particular in WO-A-96/03367 and WO-A-96/03479 are described. These reaction products are generally mixtures of pure nitropolyisobutenes (e.g. alpha,beta-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g. alpha-nitro-betahydroxypolyisobutene).

Additives containing hydroxyl groups in combination with mono- or polyamino groups (c) are, in particular, reaction products of polyisobutene epoxides, obtainable from polyisobutene preferably having predominantly terminal double bonds and having Mn = 300 to 5000, with ammonia, mono- or polyamines, as are used in particular in EP-A-476 485 are described.

Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts (d) are preferably copolymers of C ₂ -C ₄₀ -olefins with maleic anhydride having a total molar mass of 500 to 20,000, all or part of the carboxyl groups to the alkali metal or alkaline earth metal salts and one remaining Rest of the carboxyl groups are reacted with alcohols or amines. Such additives are in particular from EP-A-307 815 known. Such additives are mainly used to prevent valve seat wear and, as in the WO-A-87/01126 described, are used advantageously in combination with conventional fuel detergents such as poly(iso)buteneamines or polyetheramines.

Additives containing sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as is found in particular in EP-A-639 632 is described. Such additives serve mainly to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly(iso)buteneamines or polyetheramines.

Additives containing polyoxy-C ₂ -C ₄ -alkylene groups (f) are preferably polyethers or polyetheramines, which are obtained by reacting C ₂ -C ₆₀ -alkanols, C ₆ -C ₃₀ -alkanediols, mono- or di-C ₂ -C ₃₀ -alkylamines, C ₁ -C ₃₀ -alkylcyclohexanols or C ₁ -C ₃₀ -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are used in particular in EP-A-310 875 , EP-A-356 725 , EP-A-700 985 and US-A-4,877,416 described. In the case of polyethers, such products also have carrier oil properties. Typical examples of these are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.

Additives containing carboxylic acid ester groups (g) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those with a minimum viscosity of 2 mm ² /s at 100° C., as is the case in particular in DE-A-38 38 918 are described. Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester polyols. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol. Such products also fulfill carrier oil properties.

Additives containing groups containing hydroxyl and/or amino and/or amido and/or imido groups (h) derived from succinic anhydride are preferably corresponding derivatives of polyisobutenylsuccinic anhydride, which are obtained by reacting conventional or highly reactive polyisobutene with Mn=300 to 5000 with maleic anhydride thermal routes or via the chlorinated polyisobutene are available. Of particular interest here are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such petrol additives are particularly popular US-A-4,849,572 described.

Additives containing groups (i) produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl substituted phenols can be derived from conventional or highly reactive polyisobutene having Mn = 300 to 5000. Such "polyisobutene Mannich bases" are particularly in the EP-A-831 141 described.

For a more precise definition of the individual gasoline additives listed, reference is expressly made here to the disclosures of the above-mentioned documents of the prior art.

B2) Carrier oils and other components:

The additive formulations according to the invention can also be combined with other customary components and additives. The main ones to be mentioned here are carrier oils without a pronounced detergent effect.

Suitable mineral carrier oils are fractions obtained during petroleum processing, such as bright stock or base oils with viscosities such as those from the class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. A fraction known as "hydrocrack oil" and obtained in the refining of mineral oil (vacuum distillate cut with a boiling range of about 360 to 500°C, obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized and dewaxed under high pressure) can also be used. Mixtures of the mineral carrier oils mentioned above are also suitable.

Examples of synthetic carrier oils that can be used according to the invention are selected from: polyolefins (polyalphaolefins or polyinternal olefins), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic acid esters of long-chain alkanols.

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers with about 5 to 35 C ₃ - to C ₆ -alkylene oxide units, mostly selected from propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof. Non-limiting examples of starter alcohols suitable for this are long-chain alkanols or phenols substituted with long-chain alkyl, 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, heptadecanol and nonylphenol.

The use of the compounds (A) according to the invention can often reduce the use of carrier oils.

Examples of suitable polyolefins are olefin polymers with Mn=400 to 1800, primarily based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C ₂ -C ₄ -alkylene groups, which are obtained by reacting C ₂ -C ₆₀ -alkanols, C ₆ -C ₃₀ -alkanediols, mono- or di-C ₂ -C ₃₀ -alkylamines, C ₁ -C ₃₀ -alkylcyclohexanols or C ₁ -C ₃₀ -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, Monoamines or polyamines are available. Such products are used in particular in EPA-310 875 , EP-A-356 725 , EP-A-700 985 and US-A-4,877,416 described. For example, poly-C ₂ -C ₆ -alkylene oxide amines or functional derivatives thereof can be used as polyetheramines. Typical examples of these are tridecanol or isotridecanol butoxylates, heptadecanol or isoheptadecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.

Examples of carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, such as those in particular DE-A-38 38 918 are described. Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester polyols. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, such as di-(n- or isotridecyl) phthalate or di-(iso-heptadecyl) phthalate .

Other suitable carrier oil systems are described, for example, in DE-A-38 26 608 , DE-A-41 42 241 , DE-A-43 09 074 , EP-A-0 452 328 and EP-A-0 548 617 , which is hereby expressly referred to.

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 7 to 25, C ₃ -C ₆ -alkylene oxide units, such as selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures thereof, preferably selected from propylene oxide and i-butylene oxide units. Non-limiting examples of suitable starter alcohols are long-chain alkanols or phenols substituted with long-chain alkyl, where the long-chain alkyl radical is in particular a straight-chain or branched C ₆ -C ₁₈ -alkyl radical. Preferred examples of alkanols are decanol, tridecanol, heptadecanol and nonylphenol, particularly preferably branched decanol, tridecanol and heptadecanol.

Other suitable synthetic carrier oils are alkoxylated alkyl phenols, as in the DE-A-10 102 913 are described

B3) Other co-additives

Other customary additives are corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or on heterocyclic aromatics in the case of non-ferrous metal corrosion protection; preferred corrosion inhibitors are mono-, di- and polycarboxylic acids which have at least 12 carbon atoms, preferably at least 14, more preferably at least 16 and most preferably at least 18 carbon atoms and preferably have no other functionalities apart from hydrocarbon radicals and carboxyl groups. Examples of these are fatty acids, dimeric fatty acids, alkyl and alkenylsuccinic acids and hydrolyzed olefin-maleic anhydride copolymers, preference being given to dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), Nonadecanoic acid, arachidic acid (eicosanoic acid), behenic acid (docosanic acid), tetracosanoic acid (lignoceric acid), cerotic acid (hexacosanoic acid), triacontanoic acid (melissinic acid), palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid [(9Z)-octadec-9- enoic acid], elaidic acid [(9E)-octadec-9-enoic acid], erucic acid [(13Z)-docos-13-enoic acid], linoleic acid [(9Z,12Z)-octadeca-9,12-dienoic acid], linolenic acid [(9Z ,12Z,15Z)-octadeca-9,12,15-trienoic acid] and elaeostearic acid [(9Z,11E,13E)-octadeca-9,11,13-trienoic acid], dimeric oleic acid ( CAS: 61788-89-4 ), dodecenylsuccinic acid, dodecylsuccinic acid, Hexadecenylsuccinic acid, hexadecylsuccinic acid, polyisobutenylsuccinic acid and derivatives thereof in which the polyisobutene radical has a molecular weight of 250 to 2300, preferably 350 to 2000, more preferably 500 to 1500 and most preferably 700 to 1100, and hydrolyzed copolymers of 12 to 30 carbon atoms having α-olefins and maleic anhydride, as described for example in WO 2015/114029.

Mention should also be made of antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof, or on 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 manganese tricarbonyl; lubricity improvers (other than the triazoles of this invention) such as certain fatty acids, alkenyl succinic acid esters, bis(hydroxyalkyl) fatty amines, hydroxyacetamides, or castor oil; and dyes (markers). If necessary, amines are also added to lower the pH of the fuel.

Examples of solvents are, for example, aromatics, such as solvent naphtha, preferably naphthalene-depleted solvent naphtha, benzene, toluene, xylene, kerosene with an aromatics content of less than 50% by volume, a sulfur content of less than 10 mg/kg and a flash point according to DIN EN ISO 13736: 2000 -04 above 60 °C and higher alcohols which have a flash point according to DIN EN ISO 13736: 2000-04 above 60 °C, preferably 2-ethylhexanol or 2-propylheptanol.

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

• (A) mindestens eine Verbindung der Formel
• (B1) mindestens eine Verbindung (B1a), bei der es sich um ein Polyisobutenamin handelt, erhältlich durch Hydroformylierung und anschließender reduktiver Aminierung, ganz besonders bevorzugt mit Ammoniak, von Polyisobuten mit Mn = 300 bis 5000,
• (B2) mindestens ein Trägeröl, sowie
• (B3) mindestens einen Korrosionsinhibitor. Kraftstoffadditivkonzentrate sind zusammengesetzt wie folgt,
• (A) 1 - 50 Gew%, bevorzugt 2 - 40 Gew%, besonders bevorzugt 5 - 30 Gew%,
• (B1) 20 - 96,75 Gew%, bevorzugt 40 - 94,5 Gew%, besonders bevorzugt 60 - 89 Gew%,
• (B2) 2 - 30 Gew%, bevorzugt 3 - 25 Gew%, besonders bevorzugt 5 - 20 Gew%, sowie
• (B3) 0,25 - 10 Gew%, bevorzugt 0,5 - 7,5 Gew%, besonders bevorzugt 1 - 5 Gew%, sowie optional weitere Coadditive,

mit der Maßgabe, daß die Summe aller Komponenten immer 100 Gew% ergibt.The detergent additives (B1) mentioned with the polar groups (a) to (i) are usually added to the fuel in an amount of from 50 to 1000 ppm by weight. The other components and additives mentioned are added, if desired, in amounts customary for this purpose. contain fuel additive concentrates

• (A) at least one compound of formula
• (B1) at least one compound (B1a), which is a polyisobuteneamine, obtainable by hydroformylation and subsequent reductive amination, very particularly preferably with ammonia, of polyisobutene with Mn=300 to 5000,
• (B2) at least one carrier oil, and
• (B3) at least one corrosion inhibitor. Fuel additive concentrates are composed as follows,
• (A) 1-50% by weight, preferably 2-40% by weight, particularly preferably 5-30% by weight,
• (B1) 20-96.75% by weight, preferably 40-94.5% by weight, particularly preferably 60-89% by weight,
• (B2) 2-30% by weight, preferably 3-25% by weight, particularly preferably 5-20% by weight, and
• (B3) 0.25-10% by weight, preferably 0.5-7.5% by weight, particularly preferably 1-5% by weight, and optionally further coadditives,

with the proviso that the sum of all components is always 100% by weight.

C) fuels

The additive compositions according to the invention can be used in all conventional gasoline fuels, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition 1990, volume A16, p. 719 et seq.

Therefore, a further subject of the present invention are fuel compositions according to claim 15.

The petrol is preferably at least one petrol according to DIN EN 228.

For example, use in a gasoline with an aromatics content of no more than 60, such as no more than 42 or no more than 35% by volume and/or a sulfur content of no more than 2000, such as no more than 150 or no more than 10 ppm by weight, is possible.

The aromatics content of petrol is, for example, 10 to 50% by volume, such as 30 to 42% by volume, in particular 32 to 40% by volume, or a maximum of 35% by volume. The sulfur content of petrol is, for example, 2 to 500, such as 5 to 100 ppm by weight, or a maximum of 10 ppm by weight.

Furthermore, the gasoline can, for example, have an olefin content of up to 50% by volume, such as from 6 to 21% by volume, in particular 7 to 18% by volume; a benzene content of up to 5% by volume, such as 0.5 to 1.0% by volume, in particular 0.6 to 0.9% by volume, and/or an oxygen content of up to 25% by volume , such as up to 10% by weight or 1.0 to 2.7% by weight, in particular from 1.2 to 2.0% by weight.

In particular, petrol fuels that can be mentioned by way of example have an aromatics content of no more than 38 or 35% by volume, an olefin content of no more than 21% by volume, a sulfur content of no more than 50 or 10 ppm by weight, a benzene content of no more than 1, 0% by volume and an oxygen content of 1.0 to 2.7% by weight.

The content of alcohols and ethers in petrol can vary over a wide range. Examples of typical maximum contents are 15% by volume for methanol, 85% by volume for ethanol, 20% by volume for isopropanol, 15% by volume for tert-butanol, 20% by volume for isobutanol and ether with 5 or more carbon atoms in the molecule, 30% by volume.

The summer vapor pressure of petrol is usually a maximum of 70 kPa, in particular 60 kPa (each at 37° C.).

The RON of petrol is usually 75 to 105. A typical range for the corresponding MON is 65 to 95.

The specifications mentioned are determined using standard methods (DIN EN 228).

• (A) mindestens eine Verbindung der Formel (III),
• (B1) mindestens eine Verbindung (B1a), bei der es sich um ein Polyisobutenamin handelt, erhältlich durch Hydroformylierung und anschließender reduktiver Aminierung, ganz besonders bevorzugt mit Ammoniak, von Polyisobuten mit Mn = 300 bis 5000,
• (B2) mindestens ein Trägeröl,
• (B3) mindestens einen Korrosionsinhibitor,
• (C) mindestens einen Ottokraftstoff, sowie
  optional mindestens einen Alkohol, bevorzugt mindestens ein C₁-C₄-Alkanol, besonders bevorzugt Methanol oder Ethanol, ganz besonders bevorzugt Ethanol.

One embodiment of the present invention is represented by fuel compositions containing

• (A) at least one compound of formula (III),
• (B1) at least one compound (B1a), which is a polyisobuteneamine, obtainable by hydroformylation and subsequent reductive amination, very particularly preferably with ammonia, of polyisobutene with Mn=300 to 5000,
• (B2) at least one carrier oil,
• (B3) at least one corrosion inhibitor,
• (C) at least one petrol, and
  optionally at least one alcohol, preferably at least one C ₁ -C ₄ alkanol, particularly preferably methanol or ethanol, very particularly preferably ethanol.

The dosage is such that the compound (A) according to the invention is present in the fuel in amounts of 20-2000 ppm by weight, particularly preferably in amounts of 30-1000 ppm by weight, very particularly preferably in amounts of 40-500 ppm by weight, in particular is present in amounts of 50-300 wppm and especially in amounts of 10-100 wppm.

The contents of the other co-additives in the fuel result from the amounts specified above for the fuel additive concentrates in relation to component (A).

The percentages and ppm amounts given in this document refer to wt.% and wt.ppm unless otherwise stated.

The invention is explained in more detail by the examples described below, without being restricted thereto.

examples

• OHZ: Hydroxylzahl, bestimmt nach DIN 53240-1
• Gesamtaminzahl: Bestimmt nach DIN EN 13716:2001
• M_n: Zahlenmittleres Molekulargewicht nach DIN 55672-1
• M_w: Massenmitleres Molekulargewicht nach DIN 55672-1
• D: Polydispersität nach DIN 55672-1
• Kaliumgehalte: Bestimmt durch ICP-OES
• DMAPA: 3-(Dimethylamino)propylamin ( CAS 109-55-7 ) der Fa. BASF SE
• PO: Propylenoxid ( CAS 75-56-9 ) der Fa. BASF SE
• BuO: 1,2-Butylenoxid ( CAS 106-88-7 ) der Fa. BASF SE
• Quadrol L^® der Firma BASF SE: Ethylendiamin×4PO
• N,N,N',N'-Tetrakis(2-Hydroxypropyl)ethylendiamin, CAS 102-60-3
• DETA: Diethylentriamin der Fa. BASF SE, CAS 111-40-0
• Isotridecanol N der BASF SE, CAS 27458-92-0
• Ambosol^®: Hydratisiertes Magnesiumsilikat der Fa. PQ Corporation.
• Viskositäten und Dichten wurden mit einem Stabinger-Viskosimeter nach ASTM D7042 bestimmt.

Abbreviations, analytics and chemicals used

• OHZ: Hydroxyl number, determined according to DIN 53240-1
• Total number of amines: Determined according to DIN EN 13716:2001
• M _n : number-average molecular weight according to DIN 55672-1
• M _w : mass-average molecular weight according to DIN 55672-1
• D: Polydispersity according to DIN 55672-1
• Potassium levels: Determined by ICP-OES
• DMAPA: 3-(dimethylamino)propylamine ( CAS 109-55-7 ) from BASF SE
• PO: propylene oxide ( CAS 75-56-9 ) from BASF SE
• BuO: 1,2-butylene oxide ( CAS 106-88-7 ) from BASF SE
• Quadrol ^L® from BASF SE: ethylenediamine×4PO
• N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, CAS 102-60-3
• DETA: Diethylenetriamine from BASF SE, CAS 111-40-0
• Isotridecanol N from BASF SE, CAS 27458-92-0
• Ambosol ^® : Hydrated magnesium silicate from PQ Corporation.
• Viscosities and densities were determined using a Stabinger viscometer according to ASTM D7042.

Synthesis examples Synthesis Example 1: DMAPA×2PO

DMAPA (408.8 g; 4.0 mol) and water (4.1 g, completely desalinated) were placed in a 3.5 l pressure autoclave with a slanting blade stirrer and the stirrer was switched on. The reactor was rendered inert with nitrogen, then it was heated to 130° C. and a pressure of 2.0 bar absolute was established with nitrogen. Propylene oxide (465 g; 8.0 mol) was metered in over a period of 6 hours. The reaction was allowed to continue for 6 h at 130° C., the mixture was cooled to 50° C., the reactor was flushed with nitrogen and the product was discharged. The product was then freed from low boilers on a rotary evaporator (90° C./10 mbar/2 h).

¹ H NMR analysis in CDCl ₃ confirmed the structure.

Synthesis Example 2: DMAPA×25PO

The product from synthesis example 1 (339 g; 1.55 mol) and 50% strength aqueous KOH solution (14.5 g) were initially taken in a 3.5 l pressure autoclave with an inclined blade stirrer, and the stirrer was switched on. The system was then evacuated to a pressure of 10 mbar and heated at 105° C. for 2 h in order to distill off the water contained in the starter mixture. The reactor was rendered inert with nitrogen, then it was heated to 130° C. and a pressure of 2.0 bar absolute was established with nitrogen. Propylene oxide (2075 g, 35.7 mol) was metered in over a period of 7 hours. The reaction was allowed to continue for 10 h at 130° C., the mixture was cooled to 80° C., the reactor was flushed with nitrogen and the product was discharged. The product was freed from low boilers on a rotary evaporator (90° C./10 mbar/2 h). Then the product with 73 g Ambosol ^® mixed, stirred for 2 h at 80° C. and filtered using a pressure suction filter (Filter medium Seitz K 150 depth filter). 2412 g of the product (99.9% of theory) were obtained in the form of a yellow oil.

OOH 76.3 mg KOH/g, total amine number 67.9 mg KOH/g, _DMAPA content according to liquid chromatography <0.005%, potassium content <10 ppm, Mn 1658 g/mol, _Mw 1891 g/mol, D 1.14 , children Viscosity at 40°C 113.4 mm ² /s.

Synthesis Example 3: DMAPA×15 PO

In a manner analogous to Synthesis Example 2, DMAPA×15 PO was obtained.

OHN 99.9 mg KOH/g, M _n 1026, M _w 1185 g/mol, D 1.15, potassium content < 10 ppm.

Synthesis Example 4: Ethylenediamine×25 PO

In a manner analogous to Synthesis Example 2, ethylenediamine×25 PO was obtained by reacting Quadrol L (ethylenediamine×4PO) with 21 equivalents of PO.

OHN 121.3 mg KOH/g, total amine number 72.2 mg KOH/g, M _n 1804 g/mol, M _w 1902 g/mol, D 1.05, potassium content < 10 ppm, dyn. Viscosity at 40°C 198.4 mPas.

Synthesis Example 5: DETA5PO

In a manner analogous to Synthesis Example 1, DETA×5 PO was obtained by propoxylation of DETA.

Synthesis Example 6: DETA25 PO

In a manner analogous to Synthesis Example 2, DETAx25 PO was obtained by propoxylation of DE-TA×5 PO (Synthesis Example 5).

Synthesis Example 7: DMAPA×2BuO

DMAPA (408.8 g; 4.0 mol) was placed in a 3.5 l pressure autoclave with an inclined blade stirrer and the stirrer was switched on. The reactor was rendered inert with nitrogen, then it was heated to 120° C. and a pressure of 2.0 bar absolute was established with nitrogen. 1,2-Butylene oxide (577 g; 8.0 mol) was metered in over a period of 15 hours. The reaction was allowed to continue for 6 h at 120° C., the mixture was cooled to 50° C., the reactor was flushed with nitrogen and the product was discharged. The product was then freed from low boilers on a rotary evaporator (90° C./10 mbar/2 h).

¹ H NMR analysis in CDCl ₃ confirmed the structure.

Synthesis Example 8: DMAPA×25BuO

The product from Synthesis Example 7 (130 g; 0.528 mol) and 50% strength aqueous KOH solution (6.0 g) were placed in a 2 l pressure autoclave with an inclined blade stirrer, and the stirrer was switched on. The system was then evacuated to a pressure of 10 mbar and heated at 95° C. for 2 h in order to distill off the water present in the starter mixture. The reactor was rendered inert with nitrogen, then it was heated to 140° C. and a pressure of 2.5 bar absolute was established with nitrogen. 1,2-Butylene oxide (875 g, 12.1 mol) was metered in over a period of 14 hours. The reaction was allowed to continue for 4 h at 140° C., the mixture was cooled to 80° C. and the reactor was flushed as well nitrogen and drained the product. The product was freed from low boilers on a rotary evaporator (90° C./10 mbar/2 h). The product was then mixed with 30 g of ^Ambosol® , stirred at 80° C./100 mbar for 2 h and filtered using a pressure suction filter (Filter medium Seitz K 900 depth filter). The product was obtained in the form of a yellow oil.

_OHN 63.7 mg KOH/g, total amine number 49.7 mg KOH/g, Mn 2374 g/mol, _Mw 2550 g/mol, D 1.07.

Application examples

The following additive package formulations were produced: PIBA* [%] Carrier oil** [%] Co-additives*** [%] Synthesis Example 2 [%] Synthesis Example 3 [%] Formulation 1 44:22 26.61 29:17 - - Formulation 2 44:22 18:36 29:17 8.25 - Formulation 3 44:22 18:36 29:17 - 8.25 Formulation 4 47.24 9.73 27.03 16.00 -

The formulations were single-phase and showed no phase separations or precipitation when stored for 6 weeks at -10° C. or when stored above -5° C. for 3 months. PIBA* [%] Carrier oil**** [%] Synthesis Example 8 [%] Synthesis Example 2 [%] Formulation 5 64.52 35.48 - - Formulation 6 64.52 18.06 17.42 - Formulation 7 64.52 18.06 - 17.42 PIBA* [%] Carrier oil** [%] solvent, corrosion inhibitor Synthesis Example 2 [%] Synthesis Example 3 [%] Formulation 8 30.86 18.57 50.57 - - Formulation 9 30.01 18.06 49:15 2.78 - Formulation 10 30.01 18.06 49:15 - 2.78 * Detergent additive obtainable by hydroformylation and amination with 1000 Mn polyisobutene
** PO/BuO based carrier oil
*** Friction modifier, solvent and corrosion inhibitor
****PO based carrier oil

engine tests

• Kraftstoff: MIRO 95 OKTAN E10
• Formulierung 4 mit 1000 mg/kg: 3 × pass
• Formulierungen 5-7 mit 2325 mg/kg: 3 × pass

Use as carrier oil:
Valve sticking test in the VW Wasserboxer engine (CEC F-016-96) at -18°C:
The behavior during valve sticking was checked by investigations in the VW Wasserboxer test according to CEC F-16-T-96. A Eurosuper fuel in accordance with EN 228 was used as the base fuel. The criteria of the test specification were used to determine whether it was a "pass" (no valve sticking in three consecutive test runs) or a "fail" (valve sticking in the first, second or third of the consecutive test runs). ) took place. The valve sticking is noticeable here by the fact that the engine can only be started with a delay or not at all. In order to enable differentiation, tests were deliberately carried out in the limit area of the valve sticking to be expected. The specified dosages of the respective additives in ppm by weight (given as pure substance content, without solvent) relate to the total quantity of the petrol formulation used.

• Fuel: MIRO 95 OCTANE E10
• Formulation 4 at 1000 mg/kg: 3 x pass
• Formulations 5-7 at 2325 mg/kg: 3 x pass

Reduction of injector deposits

The engine test was performed as described in WO 2014/023853 , page 22, line 20 to page 23, line 5.

For this purpose, a commercially available, supercharged four-cylinder Otto engine (1.6 L cubic capacity) with direct injection and E0 gasoline containing 7% by volume of oxygen-containing compounds was tested using an internal method.

The fuel was admixed with 80 ppm by weight of the specified products from the synthesis examples or formulations and the FR value was determined over the running time. The FR value is a parameter created by the engine control and corresponds to the fuel injection time into the combustion chamber. If the FR value increases during the test run, this indicates deposits on the injector, the larger the increase, the more deposits have formed. On the other hand, if the FR value remains constant or even falls over the course of the remaining run, the injection nozzle remains free of deposits.

• Testlauf 1: Grundwert ohne Additiv
  Startend mit 0 sinkt der FR-Wert zunächst ab um nach ca. 30 Stunden wieder 0 zu erreichen und erreicht nach 50 Stunden Laufzeit einen Endwert von +2,60.
• Testlauf 2: Zusatz von 80 Gew.ppm der Verbindung aus Synthesebeispiel 2 in den Kraftstoff
  Startend mit 0 sinkt der FR-Wert dauerhaft ab und erreicht nach 50 Stunden Laufzeit einen Endwert von -2,00.
• Testlauf 3: Zusatz von 80 Gew.ppm der Verbindung aus Synthesebeispiel 3 in den Kraftstoff
  Startend mit 0 sinkt der FR-Wert dauerhaft ab und erreicht - zuletzt wieder leicht ansteigend - nach 50 Stunden Laufzeit einen Endwert von -1,58.
• Testlauf 4: Vergleich zu EP 700985
  Startend mit 0 mit einem unadditivierten Kraftstoff erreicht der FR-Wert nach 80 h einen Wert von 7,0 (dirty-up). Danach werden dem Kraftstoff 65 ppm PIBA und 55 ppm Polyetheramin gemäß Herstellungsbeispiel B der EP700985 (iso-C₁₃H₂₇O(CH₂CHEtO)₂₁-(CH₂CHEt)-NH₂) zugesetzt. Nach weiteren 20 h Laufzeit wird ein FR-Wert von 4,1 erreicht (clean-up). Der relative clean-up beträgt damit 41%.
• Testlauf 5: Zusatz von Synthesebeispiel 2
  Startend mit 0 mit einem unadditivierten Kraftstoff steigt der FR-Wert und erreicht nach 60 h einen Wert von 6,8 (dirty-up). Danach werden dem Kraftstoff 65 ppm PIBA, 55 ppm Trägeröl und 55 ppm Synthesebeispiel 2 zugesetzt. Nach weiteren 20 h Laufzeit wird ein FR-Wert von 2,0 erreicht (clean-up). Der relative clean-up beträgt damit 71%.

At the same time, the combustion chamber deposits are determined (deposits on the top of the piston: PTD, deposits in the cylinder head: CHD).

• Test run 1: basic value without additive
  Starting with 0, the FR value initially drops, only to reach 0 again after about 30 hours and reaches a final value of +2.60 after 50 hours of running time.
• Test Run 2: Addition of 80 ppm by weight of the compound from Synthesis Example 2 to the fuel
  Starting with 0, the FR value drops permanently and reaches a final value of -2.00 after 50 hours of running time.
• Test Run 3: Addition of 80 ppm by weight of the compound from Synthesis Example 3 to the fuel
  Starting with 0, the FR value drops permanently and finally reaches a final value of -1.58 after 50 hours of running time - finally rising again slightly.
• Test run 4: comparison to EP 700985
  Starting with 0 with an additive-free fuel, the FR value reaches a value of 7.0 (dirty-up) after 80 hours. Thereafter, 65 ppm of PIBA and 55 ppm of polyetheramine according to Preparation Example B are added to the fuel EP700985 (iso-C13 H27 O( _{CH2 CHEtO} ) ₂₁ -( _{CH2 CHEt} ) _-NH2 ) added. After a further 20 h running time, an FR value of 4.1 is reached (clean-up). The relative clean-up is thus 41%.
• Test Run 5: Addition of Synthesis Example 2
  Starting with 0 with an unadditized fuel, the FR value increases and reaches a value of 6.8 (dirty-up) after 60 hours. Thereafter, 65 ppm PIBA, 55 ppm carrier oil and 55 ppm Synthesis Example 2 are added to the fuel. After a further 20 h running time, an FR value of 2.0 is reached (clean-up). The relative clean-up is thus 71%.

Reduction of combustion chamber deposits in an M111 (PFI) engine:
Fuel MIRO E10, 95 octane; Test according to CEC F-020-98 Dosage [mg/kg] PTD ¹⁾ CHD ²⁾ Formulation 1 365 2819 1609 Formulation 2 365 2036 1071 Formulation 3 365 2244 1051 ¹⁾ Piston top deposit; ²⁾ cylinder head deposit

Reduction of combustion chamber deposits in an M111 (PFI) engine:

Fuel MIRO E10, 95 octane; Test according to CEC F-020-98 Dosage [mg/kg] PTD ¹⁾ CHD ²⁾ Formulation 8 1400 4912 1152 Formulation 9 1440 4720 940 Formulation 10 1440 4768 1007 ¹⁾ Piston top deposit; ²⁾ cylinder head deposit

Claims (15)

1. The use of compounds (A) selected from the group consisting of

   

   and formula (II)

   

   in which

   R is a divalent organic radical, preferably an alkylene radical having 2 to 10 carbon atoms,

   R¹, R², R³, R⁴, R⁵ and R⁶ are independently hydrogen or a monovalent organic radical or a -[-X_i-]_n-H radical or R¹ and R² collectively and together with the nitrogen atom may form a five- to seven-membered ring, preferably hydrogen, an alkyl radical having 1 to 20 carbon atoms or a -[-X_i-]_n-H radical,

   w is a positive integer and

   x, y and z are independently zero or a positive integer,

   - in which n is a positive integer, and

   - in which each X_i for i = 1 to n is independently selected from the group consisting of -CH₂-CH₂-O-, - CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, - C(CH₃)₂-CH₂-O-, -CH₂-CH(C₂H₅)-O-, -CH(C₂H₅)-CH₂-O- and

   - CH(CH₃)-CH(CH₃)-O-, preferably selected from the group consisting of -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -CH₂-CH(C₂H₅)-O-,

   - CH(C₂H₅)-CH₂-O- and -CH(CH₃)-CH(CH₃)-O-, more preferably selected from the group consisting of - CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, - C (CH₃)₂-CH₂-O-, -CH₂-CH(C₂H₅)-O- and -CH(C₂H₅)-CH₂-O- and most preferably selected from the group consisting of -CH₂-CH(C₂H₅)-O-, -CH(C₂H₅)-CH₂-O-, - CH₂-CH(CH₃)-O- and -CH(CH₃)-CH₂-O-, and especially selected from the group consisting of -CH₂-CH(CH₃)-O- and -CH(CH₃)-CH₂-O-,

   with the proviso that

   - the sum total of x, y and z is non-zero,

   - at least one of the R¹, R², R³, R⁴, R⁵ and R⁶ radicals is not hydrogen and

   - at least one of the R¹, R², R³, R⁴, R⁵ and R⁶ radicals represents a -[-X_i-]_n-H radical,

   in gasoline fuels for avoidance and/or reduction of the formation of deposits at injection nozzles in direct injection gasoline engines and/or removing and/or reducing existing deposits at injection nozzles in direct injection gasoline engines.
2. The use according to claim 1, wherein the R radical is selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene and 1,10-decylene.
3. The use according to any of the preceding claims, wherein R¹, R², R³, R⁴, R⁵ and R⁶, if they do not represent a -[-X_i-]_n-H radical, are independently selected from the group consisting of hydrogen and an alkyl radical having 1 to 12 carbon atoms.
4. The use according to claim 3, wherein R¹, R², R3, R⁴, R⁵ and R⁶, if they do not represent a -[-X_i-]_n-H radical, are independently selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl and tert-butyl.
5. The use according to any of the preceding claims, wherein the compound is a compound of the formula (I) .
6. The use according to claim 5, wherein x = 1 or 2 and R is 1,2-ethylene, 1,2-propylene or 1,3-propylene.
7. The use according to claim 5 or 6, wherein R¹ and R² are each independently C₁- to C₄-alkyl and R³ and R⁴ are each independently a -[-X_i-]_n-H radical.
8. The use according to claim 7, wherein each X_i for i = 1 to n is independently selected from the group consisting of -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -CH₂-CH(C₂H₅)-O- and - CH(C₂H₅)-CH₂-O-.
9. The use according to any of the preceding claims, wherein the compound (A) satisfies the formula (III)

   

   in which

   R¹, R² and X_i have the definitions given above and

   p and q are independently a positive integer.
10. The use according to claim 9, wherein the sum total of p and q is from 2 to 50.
11. The use according to claim 1, wherein the radicals in formula (I) are defined as follows:

    (Ia) R is 1,2-ethylene, w = 1, R¹ to R³ are methyl and R⁴ is a -[-X_i-]_n-H chain

    (Ib) R is 1,2-ethylene, w = 1, R¹ and R² are methyl and R³ and R⁴ are each independently a -[-X_i-]_n-H chain

    (Ic) R is 1,2-propylene, w = 1, R¹ and R² are methyl and R³ and R⁴ are each independently a -[-X_i-]_n-H chain

    (Id) R is 1,3-propylene, w = 1, R¹ and R² are methyl and R³ and R⁴ are each independently a -[-X_i-]_n-H chain

    (Ie) R is 1,3-propylene, w = 1, R¹ and R² are ethyl and R³ and R⁴ are each independently a -[-X_i-]_n-H chain,

    (If) R is 1, 3-propylene, w = 1, R¹ and R² are n-butyl and R³ and R⁴ are each independently a -[-X_i-]_n-H chain, and

    (Ig) R is 1,2-ethylene, w = 1, R¹ to R⁴ are a -[-X_i-]_n-H chain.
12. The use according to claim 1, wherein the radicals in formula (II) are defined as follows:

    (IIa) R is 1,2-ethylene, x and y are 1, z = 0 and R¹ to R⁴ and R⁶ are each independently a -[-X_i-]_n-H chain

    (IIb) R is 1,2-propylene, x and y are 1, z = 0 and R¹ to R⁴ and R⁶ are each independently a -[-X_i-]_n-H chain, and

    (IIc) R is 1,3-propylene, x and y are 1, z = 0 and R¹ to R⁴ are each independently a -[-X_i-]_n-H chain, and R⁶ is C₁- to C₂₀-alkyl.
13. The use according to claim 9, wherein the radicals in formula (III) are defined as follows:

    (IIIa) R is 1,2-ethylene and R¹ and R² are methyl

    (IIIb) R is 1,2-ethylene and R¹ and R² are ethyl

    (IIIc) R is 1,2-ethylene and R¹ and R² are n-butyl

    (IIId) R is 1,2-ethylene and R¹ and R² are collectively a 1,4-butylene chain

    (IIIe) R is 1,2-ethylene and R¹ and R² are collectively a 1,5-pentylene chain

    (IIIf) R is 1,2-ethylene and R¹ and R² are collectively a 3-oxa-1,5-pentylene chain

    (IIIg) R is 1,2-propylene and R¹ and R² are methyl

    (IIIh) R is 1,2-propylene and R¹ and R² are ethyl

    (IIIi) R is 1,2-propylene and R¹ and R² are n-butyl

    (IIIj) R is 1,2-propylene and R¹ and R² are collectively a 1,4-butylene chain

    (IIIk) R is 1,2-propylene and R¹ and R² are collectively a 1,5-pentylene chain

    (IIIl) R is 1,2-propylene and R¹ and R² are collectively a 3-oxa-1,5-pentylene chain

    (IIIm) R is 1,3-propylene and R¹ and R² are methyl

    (IIIn) R is 1,3-propylene and R¹ and R² are ethyl

    (IIIo) R is 1,3-propylene and R¹ and R² are n-butyl

    (IIIp) R is 1,3-propylene and R¹ and R² are collectively a 1,4-butylene chain

    (IIIq) R is 1,3-propylene and R¹ and R² are collectively a 1,5-pentylene chain, and

    (IIIr) R is 1,3-propylene and R¹ and R² are collectively a 3-oxa-1,5-pentylene chain.
14. A fuel additive concentrate comprising

    (A) 1-50% by weight of at least one compound of the formula (I), (II) or (III) as described in any of claims 1 to 13,

    in which each X_i for i = 1 to n is independently selected from the group consisting of -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -CH₂-CH(C₂H₅)-O- and -CH(C₂H₅)-CH₂-O-, and

    in which the compound (A) satisfies the formula (III)

    

    in which

    R¹, R² and X_i have the definitions given above and

    p and q are independently a positive integer,

    (B1) 20-96.75% by weight of at least one compound (B1a) which is a polyisobuteneamine obtainable by hydroformylation and subsequent reductive amination, most preferably with ammonia, of polyisobutene with Mn = 300 to 5000,

    (B2) 2-30% by weight of at least one carrier oil selected from the group consisting of polyolefins, (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic esters of alkanols having 6 to 24 carbon atoms, and

    (B3) 0.25-10% by weight of at least one corrosion inhibitor selected from the group consisting of mono-, di- and polycarboxylic acids having at least 12 carbon atoms, ammonium salts of organic carboxylic acids and heterocyclic aromatics, with the proviso that the sum total of all components is always 100% by weight.
15. A fuel composition comprising

    (A) 20 to 2000 ppm by weight of at least one compound of the formula (I), (II) or (III) as described in any of claims 1 to 13,

    in which each X_i for i = 1 to n is independently selected from the group consisting of -CH₂-CH(CH₃)-O-, -CH(CH₃)-CH₂-O-, -CH₂-C(CH₃)₂-O-, -C(CH₃)₂-CH₂-O-, -CH₂-CH(C₂H₅)-O- and -CH(C₂H₅)-CH₂-O-, and

    in which the compound (A) satisfies the formula (III)

    

    in which

    R¹, R² and X_i have the definitions given above and

    p and q are independently a positive integer,

    (B1) 50 to 1000 ppm by weight of at least one compound (B1a) which is a polyisobuteneamine obtainable by hydroformylation and subsequent reductive amination, most preferably with ammonia, of polyisobutene with Mn = 300 to 5000,

    (B2) at least one carrier oil selected from the group consisting of polyolefins, (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic esters of alkanols having 6 to 24 carbon atoms, (B3) at least one corrosion inhibitor selected from the group consisting of mono-, di- and polycarboxylic acids having at least 12 carbon atoms, ammonium salts of organic carboxylic acids and heterocyclic aromatics,

    (C) at least one gasoline fuel, and
    optionally at least one alcohol, preferably at least one C₁-C₄-alkanol, more preferably methanol or ethanol, most preferably ethanol.