DE102022131890A1 - Guanidine derivatives as fuel additives - Google Patents

Abstract

The present invention describes guanidine derivatives as fuel additives to reduce injector deposits in direct injection diesel and gasoline engines.

Description

The present invention describes guanidine derivatives as fuel additives to reduce injector deposits in direct injection diesel and gasoline engines.

It is known that quaternary nitrogen compounds can be used as additives to remove deposits, particularly in injectors in diesel or gasoline engines, see, for example, described in WO 2013/070503 A1 or WO 2014/195464 A1 .

The disadvantage, however, is that quaternary nitrogen compounds in fuels act as emulsifiers and have a negative effect on water separation and foam formation.

Out WO 2012/72723 reaction products from hydrocarbyl-substituted dicarboxylic acids and aminoguanidines and their use as additives to reduce fuel consumption in diesel fuels or gasoline are known.

The object of the present invention was to provide compounds with which the formation of deposits on injection nozzles can be avoided or reduced in direct-injection diesel and Otto engines and/or existing deposits can be removed without impairing the separation of water from fuels.

worin
R¹ bis R⁴ jeweils unabhängig voneinander einen einbindigen organischen Rest, bevorzugt C₁-bis C₄-Alkyl, besonders bevorzugt Methyl oder Ethyl und ganz besonders bevorzugt Methyl, und R⁵ einen einbindigen, 8 bis 100 Kohlenstoffatome aufweisenden organischen Rest,
wobei R¹ und R² bzw. R³ und R⁴ jeweils unabhängig voneinander auch gemeinsam mit dem Stickstoffatom der Gruppe -NR¹R² bzw. -NR³R⁴ einen fünf- bis siebengliedrigen Ring bilden, bedeuten können,
in Diesel- und Ottokraftstoffen zur Vermeidung und/oder Verringerung der Bildung von Ablagerungen an Einspritzdüsen in direkteinspritzenden Diesel- und Ottomotoren und/oder Entfernung und/oder Verringerung von bestehenden Ablagerungen an Einspritzdüsen in direkteinspritzenden Diesel- und Ottomotoren.The object was achieved by using guanidine derivatives (A) of the formula (III)

wherein
R ¹ to R ⁴ are each independently a monovalent organic radical, preferably C ₁ - to C ₄ -alkyl, particularly preferably methyl or ethyl and very particularly preferably methyl, and R ⁵ is a monovalent organic radical having 8 to 100 carbon atoms,
where R ¹ and R ² or R ³ and R ⁴ each independently of one another together with the nitrogen atom of the group -NR ¹ R ² or -NR ³ R ⁴ can form a five- to seven-membered ring,
in diesel and petrol fuels to prevent and/or reduce the formation of deposits on injector nozzles in direct injection diesel and petrol engines and/or remove and/or reduce existing deposits on injector nozzles in direct injection diesel and petrol engines.

Furthermore, the alkylated guanidine derivatives mentioned can be used to avoid and/or reduce the formation of deposits and/or remove and/or reduce existing deposits on intake or exhaust valves, as well as combustion chamber deposits on the piston surface and/or on the cylinder head of diesel and gasoline engines.

The alkylated guanidine derivatives prevent or remove the formation of deposits on the injectors of direct-injection spark-ignition engines and show a better water separation capacity than the reaction products of aminoguanidines according to WO 2012/72723 .

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 preferably methyl and ethyl and most preferably methyl.

Preferred monovalent organic radicals containing 8 to 100 carbon atoms are straight-chain or branched C ₈ - to C ₁₀₀ -alkyl.

Examples thereof are n-octyl, 2-ethylhexyl, n-decyl, 2-propylheptyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-heptadecyl, iso-heptadecyl, n-octadecyl and n -eicosyl.

R ¹ is preferably methyl or ethyl, particularly preferably methyl.

R ² is preferably methyl or ethyl, particularly preferably methyl.

R ¹ and R ² are particularly preferably the same.

R ³ is preferably methyl or ethyl, particularly preferably methyl.

R ⁴ is preferably methyl or ethyl, particularly preferably methyl.

R ³ and R ⁴ are particularly preferably the same.

In a preferred embodiment, the radicals R ¹ to R ⁴ are all the same.

If the radicals R ¹ and R ² or R ³ and R ⁴ together with the nitrogen atom of the group -NR ¹ R ² or -NR ³ R ⁴ form a five- to seven-membered ring, these can preferably be pyrrolidine, act piperidine or morpholine.

In a preferred embodiment, the radical R ⁵ is a linear alkyl group with an even number of carbon atoms, selected from the group consisting of n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n- eicosyl.

In a further preferred embodiment, the radical R ⁵ is a mixture of branched alkyl groups having 13 or 17 carbon atoms, particularly preferably one which is obtainable by hydroformylation from a C ₁₆ -olefin mixture which in turn is obtainable by oligomerization of an olefin mixture , which contains predominantly hydrocarbons having four carbon atoms.

Such an alkyl group R ⁵ preferably has an average degree of branching, measured as the ISO index, of 1.8 to 3.7.

In another embodiment, the R ⁵ group is a hydrophobic hydrocarbon group having a number average molecular weight (M _n ) of from 85 to 1500, preferably from 113 to 1450, more preferably from 126 to 1400, more preferably from 169 to 1350 more preferably from 211 to 1300 and in particular from 225 to 1200, especially from 550 to 1100. Such a hydrophobic hydrocarbon radical is preferably a radical derived from polypropenyl, polybutenyl and polyisobutenyl and having the corresponding number average molecular weight M _n , obtainable by polymerizing olefin mixtures containing propene, butene or isobutene, preferably by polymerizing olefin mixtures containing propene or isobutene and particularly preferably isobutene.

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

1. (A) mindestens eine Verbindung der Formel (III), sowie
2. (B) mindestens eine weitere Additivkomponente.

Another subject of the present invention are fuel additive concentrates containing

1. (A) at least one compound of formula (III), and
2. (B) at least one further additive component.

manufacturing

The production of such guanidine derivatives is known in principle, for example starting from the corresponding ureas R ¹ R ² N-(CO)-NR ³ R ⁴ and the primary amines R ⁵ -NH ₂ as described in Willi Kantlehner, Jochen Mezger, Ralf Kress , Horst Hartmann, Thorsten Moschny, Ionnis Tiritiris, Boyan Iliev, Oliver Scherr, Georg Ziegler, Bahari Souley, Wolfgang Frei, Ivo C. Ivanov, Milen G. Bogdanov, Ulrich Jäger, Günther Dospil and Tillmann Viefhaus, Z. Naturforsch. 2010, 65b, 873-906.

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 lonescu, 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 using regenerable ion exchangers, in which case the alkylated guanidine derivative can also be dissolved in a solvent.

Preferred amines R ⁵ -NH ₂ are selected from the group consisting of fatty amines, branched amines and polyolefin amines.

Examples of fatty amines are amines obtainable from hydrogenation and amination of fatty acids or mixtures of fatty acids such as can be obtained from naturally occurring fats and oils.

Preferred fatty amines are those amines obtainable from fatty acids such as stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid and linolenic acid.

Industrially customary fatty acid mixtures are preferably tallow fatty acid, coconut oil fatty acid, trans fatty acid, coconut palm kernel oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid or palm oil fatty acid, which contain oleic acid and palmitic acid as main components.

n-Decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and n-eicosylamine, and mixtures thereof, are particularly preferred.

Examples of branched amines R ⁵ -NH ₂ are primary amines with an alkyl group R ⁵ with 8 to 22, preferably from 10 to 17, more preferably 13 to 17, most preferably 13 or 17 carbon atoms, the alkyl group having a branch of at least 1 .0, preferably from 1.0 to 8.0, particularly preferably from 1.5 to 7.0.

"Branch" in the context of the present invention means that the alkyl radical R ⁵ comprises the required number of branches. In the case of a single amine with only one branched isomer, the branching of this pure compound can be readily determined from the chemical structure. For mixtures of isomers, the average branching of the mixture is calculated by adding the branching of each individual isomer times the molar amount of each isomer in the mixture. Preferably, branching is determined using the branching index (ISO index) as described in WO 2022/161803 , there especially page 5, line 1 to page 6, line 11.

The branched primary amines can be used as a mixture of amines of different molecular weights or, preferably, a single molecular weight.

Typical examples of such amines are the branched isomers of octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine and heptadecylamine, preferably nonylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, eicosylamine, docosylamine, and mixtures thereof , particularly preferably nonylamine, tridecylamine and heptadecylamine, most likely tridecylamine and heptadecylamine and especially tridecylamine.

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

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

In a preferred embodiment, the branched amines according to the present invention are obtainable by oligomerization of propene, isobutene, 1-butene or 2-butene to form a double bond-containing oligomer, followed by hydroformylation and reductive amination with ammonia. The resulting amine is usually a mixture of isomers.

In a further preferred embodiment, the branched amines of the present invention can be obtained by amination of the corresponding branched alcohols or by reductive amination of the corresponding branched aldehydes. In this case, the branching of the resulting amines is the same as that of the starting alcohols or aldehydes since the reaction conditions of the amination or reductive amination do not normally affect the branching of the alkyl group.

• 2,2,4,4,6,6-Hexamethylheptylamin, 2,4,6-Triethylheptylamin, 2,3,4,5,6-Pentamethyloctylamin, Heptylamine mit 2 Ethylgruppen und 2 Methylgruppen in Position 2, 4 und 6 und Heptylamine mit 1 Ethylgruppe und 4 Methylgruppen in Position 2, 4 und 6.

In the case of branched tridecylamine, the mixture of isomers may contain one or more of the following isomers:

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

Isomer mixtures with 2,2,4,4,6,6-hexamethylheptylamine or 2,4,6-triethylheptylamine as main components are particularly preferred.

Examples of mixtures of such branched amines are mixtures of tertiary alkyl C12 to C14 amines ( _CAS No. _68955-53-3 ) or of _C16 to _C22 amines obtainable by the Ritter reaction.

Among the branched primary alkylamines, preference is therefore given to those amines having the amine group bonded to a primary carbon, ie amines which carry a —CH ₂ NH ₂ group.

A mixture of tridecylamine isomers from BASF SE (CAS No.: 86089-17-0), which is obtained by amination from the corresponding tridecanol isomer mixture with a branching index of 2.2, is particularly preferred.

Also preferred is a mixture of heptadecylamine isomers obtained by amination from the corresponding heptadecanol isomer mixture having a branching index of 2.8 to 3.7.

In a further preferred embodiment, the polyolefin amines can be obtained by polymerizing propene, isobutene, 1-butene or 2-butene, preferably isobutene, to form a polymer containing double bonds, preferably polyisobutene, followed by hydroformylation and reductive amination with ammonia.

In a particularly preferred embodiment, it is polyisobuteneamine (CAS No. 886464-29-5), obtainable from highly reactive polyisobutene (Mn=1000) after hydroformylation and amination with ammonia. The hydroformylation/amination process is described in WO 2004/87808 . This is commercially available, for example, as Kerocom(R) PIBA from BASF.

B) Other additive components

The compounds (A) 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).

In the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the described copolymers, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators , dyes and/or solvents.

In the case of petrol, these are primarily detergent additives, lubricity improvers (friction modifiers), corrosion inhibitors other than the copolymers described, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and/or solvents.

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 .

• Mono- oder Polyaminogruppen (a) enthaltende Additive sind vorzugsweise Polyalkenmono- oder Polyalkenpolyamine auf Basis von Polypropen oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit Mn = 300 bis 5000. Geht man bei der Herstellung der Additive von Polybuten oder Polyisobuten mit überwiegend mittenständigen Doppelbindungen (meist in der beta-und gamma-Position) aus, bietet sich der Herstellweg durch Chlorierung und anschließende Aminierung oder durch Oxidation der Doppelbindung mit Luft oder Ozon zur Carbonyl- oder Carboxylverbindung und anschließende Aminierung unter reduktiven (hydrierenden) Bedingungen an. Zur Amin ierung können hier Amine, wie z.B. Ammoniak, Monoamine oder Polyamine, wie Dimethylaminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin, eingesetzt werden. Entsprechende Additive auf Basis von Polypropen sind insbesondere in der WO-A-94/24231 beschrieben.

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, for example, ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be used for the amination here. Corresponding additives based on polypropylene are described in particular in WO-A-94/24231.

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

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 described in particular in WO-A-96/ 03367 and WO-A-96/03479. These reaction products are usually 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, the carboxyl groups of which are wholly or partially to the alkali metal or alkaline earth metal salts and a remainder of the carboxyl groups are reacted with alcohols or amines. Such additives are in particular from EP-A-307 815 known. Additives of this type serve mainly to prevent valve seat wear and, as described in WO-A-87/01126, can advantageously be used 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 are available. Such products are described 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 described 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.

• Die erfindungsgemäßen Additiv-Formulierungen können darüber hinaus mit noch weiteren üblichen Komponenten und Additiven kombiniert werden. Hier sind in erster Linie Trägeröle ohne ausgeprägte Detergenswirkung zu nennen.

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) 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 found in particular in E PA-310 875 , EP-A-356 725, EP-A-700 985 and US-A-4,877,416. For example, poly-C ₂ -C ₆ -alkylene oxide amines or functional derivatives thereof can be used as polyether amines. 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, as are described in particular in DE-A-38 38 918. 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 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 described in DE-A-10 102 913

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 except hydrocarbon residues and carboxyl groups have no further functionalities. 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 re and derivatives thereof in which the polyisobutene radical has a molecular weight of from 250 to 2300, preferably from 350 to 2000, more preferably from 500 to 1500 and most preferably from 700 to 1100, and hydrolyzed copolymers of 12 to 30 carbon atoms α-olefins and maleic anhydride, as for example in WO 2015/114029 are described.

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 triazoles) 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.

The detergent additives (B1) mentioned with the polar groups (a) to (i) are usually added to the fuel in an amount of 10 to 5000 ppm by weight, in particular 50 to 1000 ppm by weight. The other components and additives mentioned are added, if desired, in amounts customary for this purpose.

A preferred embodiment represent fuel additive concentrates containing
(A) at least one compound of formula (III),
(B1) at least one compound with detergent action, preferably at least one compound (B1a), more preferably at least one compound (B1a), which is a polyisobuteneamine, obtainable by hydroformylation and subsequent reductive amination, most preferably with ammonia, from polyisobutene with Mn = 300 to 5000,
(B2) at least one carrier oil, and
(B3) at least one corrosion inhibitor.

The fuel additive concentrates are particularly preferably 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 co-additives,
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 containing
(A) at least one compound of formula (III),
(B) at least one further additive component, and
(C) at least one fuel, preferably at least one petrol, particularly 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 aromatic 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 preferred embodiment of the present invention are fuel compositions containing
(A) at least one compound of formula (III),
(B1) at least one compound with detergent action, preferably at least one compound (B1a), more preferably at least one compound (B1a), which is a polyisobuteneamine, obtainable by hydroformylation and subsequent reductive amination, most preferably with ammonia, from 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 qualities of diesel fuels are specified in more detail, for example, in EN 590 (cf. also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, volume A12, p. 617 et seq.).

The use according to the invention in middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, also relates to mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are encompassed by the term "middle distillate fuel". They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 50 wt .-%, preferably 2 to 30 wt .-% and in particular from 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.

Fuels are also conceivable which contain biofuel oils to a greater extent or even consist of them, for example more than 50% by weight, preferably at least 60% by weight, particularly preferably at least 70% by weight, very particularly preferably at least 80% by weight and even 100% by weight (B100).

Biofuel oils are typically based on fatty acid esters, preferably essentially on alkyl esters, of fatty acids derived from vegetable and/or animal oils and/or fats. Alkyl esters are usually understood as meaning lower alkyl esters, preferably C ₁ - to C ₄ -alkyl esters, particularly preferably methyl or ethyl ester and very particularly preferably methyl ester, which are obtained by transesterification of the glycerides, in particular triglycerides, occurring in vegetable and/or animal oils and/or fats are available using lower alcohols, for example ethanol or, above all, methanol (“FAME”). Typical lower alkyl esters based on vegetable and/or animal oils and/or fats that are used as biofuel oil or components thereof are, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME"), animal fat methyl ester ("FME") or tallow methyl ester (“TME”), methyl esters of recovered vegetable oils, recycled used cooking oils and frying fats, so-called used vegetable oil (“UVO”) or waste vegetable oil (“WVE”) or used cooking oil methyl ester ( "UCOME"), tall oil methyl ester and in particular rapeseed oil methyl ester ("RME").

The middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001% by weight sulphur.

The dosage is such that the compound (A) according to the invention is present in the fuel in amounts of 10-5000 ppm by weight, preferably in amounts of 20-2000 ppm by weight, particularly preferably in amounts of 30-1000 ppm by weight in amounts of 40 - 500 wppm, in particular 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

Synthesis example 1:

N,N,N',N'-Tetramethyl-N"-octylguanidine

This is compound 9e as described in Willi Kantlehner, Jochen Mezger, Ralf Kreß, Horst Hartmann, Thorsten Moschny, Ionnis Tiritiris, Boyan Iliev, Oliver Scherr, Georg Ziegler, Bahari Souley, Wolfgang Frei, Ivo C. Ivanov, Milen G Bogdanov, Ulrich Jäger, Günther Dospil and Tillmann Viefhaus, Z. Naturforsch. 2010, 65b, 873-906.

The NMR data confirm the expected structure.
¹ H-NMR (200 MHz, CDCl ₃ ): δ = 0.82-0.85 (m, 3H, N-(CH ₂ ) ₇ -CH ₃ ), 1.20-1.40 (m, 10H, -CH ₂ -), 1.41- 1.60 (m, 2H, N-CH ₂ -CH ₂ -), 2.65 (s, 6H, N-CH ₃ ), 2.80 (s, 6H, N-CH ₃ ), 3.10 (t, J=Hz, 2H, N-CH ₂ C ₇ H ₁₅ )

Application examples

Avoidance of deposits

An E0 fuel, which leads to deposits in direct-injection Otto engines (DISI engines, direct injection spark ignition), was used as the fuel.

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

For this purpose, a commercially available, supercharged four-cylinder gasoline engine (1.6 L cubic capacity) with direct injection was operated with the E0 gasoline described above.

The specified additives were added to the fuel and the FR value was determined over a period of time. The FR value is a parameter created by the engine control and corresponds to the injection time of the fuel 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. If, on the other hand, the FR value remains constant or even falls over the course of the remaining run, the injection nozzle remains free of deposits.

Test run 1: basic value without additive (Figure 1)

Starting with 0, the FR value rises very briefly, then falls and reaches 0 again after about 10 hours. After continuous increase, the FR value reaches 3.35% after 48h.

Test run 2 (comparison): Addition of 40 ppm by weight of a doubly ethoxylated coconut amine in the fuel (Figure 2):

Starting at 0, the FR value decreases and reaches zero again after 25 h to an endpoint of 2.74%

Test run 3 (according to the invention): addition of 40 ppm by weight of the product from synthesis example 1 in the fuel (FIG. 3):

Starting at 0, the FR value decreases and after 18 h reaches a tableau with an endpoint of -3.47%

water separation

As part of a polyisobuteneamine-containing additive package, the compounds listed in the table below were subjected to a water separation test according to ASTM D 1094 in E0 fuel, the phase separation and the interface being evaluated after 15 minutes. Dosage [mg/kg] Rating Interphase Rating Separation PIBSA-aminoguanidine(*) 20 2 2 Synthesis example 1 20 1b 1
(*) It is the reaction product of polyisobutenylsuccinic acid with aminoguanidine in a 1:1 ratio, according to WO 2012/072723 .

QUOTES INCLUDED IN DESCRIPTION

This list of the documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• WO 2014195464 A1 [0002]
• WO 201272723 [0004, 0008]
• WO 2022161803 [0034]
• WO 200487808 [0048]
• DE 19620262 A [0056]
• EP 476485A [0058]
• EP 307815 A [0059]
• EP 639632 A [0060]
• EP 700985 A [0061, 0072]
• US4877416A [0061]
• US4849572A [0063]
• EP 831141A [0064]
• PA310875 [0072]
• EP0452328A [0074]
• EP0548617A [0074]
• WO 2015114029 [0077]
• WO 2012072723 [0113]

Claims (12)

Use of guanidine derivatives (A) of formula (III)

where R ¹ to R ⁴ are each independently a monovalent organic radical, preferably C ₁ - to C ₄ -alkyl, particularly preferably methyl or ethyl and very particularly preferably methyl, and R ⁵ is a monovalent organic radical having 8 to 100 carbon atoms, where R ¹ and R ² or R ³ and R ⁴ can each independently form a five- to seven-membered ring together with the nitrogen atom of the group -NR ¹ R ² or -NR ³ R ⁴ , in diesel and gasoline fuels to prevent and/or reduce the formation of deposits on injector nozzles in direct injection diesel and petrol engines and/or remove and/or reduce existing deposits on injector nozzles in direct injection diesel and petrol engines. use according to claim 1 , characterized in that R ¹ and R ² are independently methyl or ethyl. use according to claim 1 or 2 , characterized in that R ³ and R ⁴ are independently methyl or ethyl. Use according to any of Claims 1 until 3 , characterized in that R ⁵ is a linear alkyl group having an even number of carbon atoms, preferably selected from the group consisting of n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n -Eicosyl. Use according to any of Claims 1 until 3 , characterized in that R ⁵ is a mixture of branched 13 or 17 carbon atom alkyl groups. use according to claim 5 , characterized in that the average degree of branching, measured as the ISO index, of the alkyl group R ⁵ is from 1.8 to 3.7. use according to claim 5 , characterized in that the alkyl group R ⁵ has from 8 to 22 carbon atoms and a branching of at least 1.0. Use according to any of Claims 1 until 3 , characterized in that R ⁵ is a hydrocarbyl group having a number average molecular weight (M _n ) of from 85 to 1,500. use according to claim 8 , characterized in that the hydrocarbyl radical is derived from polypropenyl, polybutenyl and polyisobutenyl. Fuel additive concentrates containing (A) at least one compound of the formula (III) as described in any of Claims 1 until 9 , (B) at least one further additive component selected from the group consisting of detergent additives, carrier oils, corrosion inhibitors, antioxidants, stabilizers and solvents. Gasoline compositions containing (A) at least one compound of formula (III) as described in any of Claims 1 until 9 , (B) at least one further additive component selected from the group consisting of detergent additives, carrier oils, corrosion inhibitors, antioxidants, stabilizers and solvents, (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. Diesel compositions containing (A) at least one compound of formula (III) as described in any of Claims 1 until 9 , (B) at least one further additive component selected from the group consisting of detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the described copolymers, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, Antistats, metallocenes, metal deactivators, dyes and/or solvents, (C) at least one diesel fuel and optionally at least one alkyl ester of fatty acids derived from vegetable and/or animal oils and/or fats.

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