EP1495096B1 - Fuel additive mixtures for gasolines with synergistic ivd performance - Google Patents

Abstract

Novel fuels for gasoline engines comprise a synergistic mixture of a detergent additive component (A) and a synthetic carrier oil component (B), i) the detergent additive component (A) comprising at least one compound having a basic nitrogen atom which is substituted by a hydrocarbyl radical having a number average molecular weight of from about 500 to 1 300, and the detergent additive component (A) being contained in the fuel in an amount of from about 30 to 180 ppm by weight; and ii) the carrier oil component (B) comprising at least one compound of the following formula I R-O-(A-O)x-H (I) where R is a straight-chain or branched C6-C18-alkyl group; A is a C3- or C4-alkylene group; and x is an integer from 5 to 35; the carrier oil component (B) being contained in the fuel in an amount of from about 10 to 180 ppm by weight.

Description

The invention relates to the use of synergistically acting gasoline fuel additive compositions with synergistic performance in the intake system purity for the addition of fuels for gasoline engines.

Carburettors and intake systems of gasoline engines, but also injection systems for fuel metering are increasingly burdened by impurities caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the guided into the carburetor crankcase vent gases.

These residues shift the air-fuel ratio at idle and in the lower part-load range, so that the mixture leaner, the incomplete combustion and turn the proportions of unburned or partially combusted hydrocarbons in the exhaust gas and gasoline consumption increases.

It is known that to avoid these disadvantages, fuel additives are used for keeping valves and carburetors or injection systems of gasoline engines clean (cf., for example: M. Rossenbeck in Catalysts, Surfactants, Mineral Oil Additives, Ed. J. Falbe, U. Hasserodt, p. 223, G. Thieme Verlag, Stuttgart 1978 ).

Depending on the mode of action but also on the preferred site of action of such detergent additives, a distinction is made today between two generations.

The first additive generation could only prevent the formation of deposits in the intake system, but not remove already existing deposits, whereas the modern additives of the second generation can cause both (keep-clean and clean-up effect) and especially because of their excellent thermal stability at higher temperature zones, namely at the inlet valves. Such detergents which can come from a variety of chemical classes of substances, such as polyalkeneamines, polyetheramines, polybutene Mannich bases or Polybutensuccinimide, are generally used in combination with carrier oils and sometimes other additive components, such as corrosion inhibitors and demulsifiers, for use. The carrier oils perform a solvent or wash function in combination with the detergents. Carrier oils are typically high boiling, viscous, thermostable liquids which coat the hot metal surface thereby preventing the build-up of impurities on the metal surface.

1. a) mineralölbasierend (d.h. es werden nur mineralölbasierende (mineralische) Trägeröle verwendet),
2. b) vollsynthetisch (d.h. es werden nur synthetische Trägeröle verwendet) oder in untergeordnetem eingesetzten Maße
3. c) semisynthetisch (d.h. es werden Mischungen aus mineralölbasierenden und synthetischen Trägerölen verwendet).

Such formulations of detergents with carrier oils can in principle be classified as follows (depending on the nature of the carrier oil (carrier oil):

1. a) Mineral oil-based (ie only mineral oil-based (mineral) carrier oils are used),
2. b) fully synthetic (ie only synthetic carrier oils are used) or in subordinate dimensions
3. c) semi-synthetic (ie mixtures of mineral oil-based and synthetic carrier oils are used).

It is known from the prior art that the described additive formulations are used in gasoline fuels. It is generally true that fully synthetic additive packages have slightly better retention properties than mineral oil-based.

The EP-A-0 704 519 describes additive mixtures for fuels comprising at least one amine having a hydrocarbon radical with an average molecular weight of 500 to 10,000, at least one hydrocarbon polymer having an average molecular weight of 300 to 10,000 in hydrogenated or nonhydrogenated form and as a carrier oil component based on a mixture of polyethers of propylene oxide and / or butylene oxide and esters of mono- or polycarboxylic acids and alkanols or polyols. In a comparative example disclosed therein, gasoline with polyisobuteneamine (molecular weight about 1000) and an isotridecanol reacted with 22 mol of butylene oxide are additized in amounts of 300 ppm each. A possible synergistic interaction of carrier oil and detergent additive is not referred to in this document.

The EP-A-0 548 617 describes gasoline fuels which are additized with an additive combination of 10 to 5000 ppm of a nitrogen-containing detergent additive and 10 to 5000 ppm of a phenol-initiated propoxylate. In a single comparative example a mixture of polyisobutylamine and an unspecified alcohol butoxylate is described. A fuel is additized with 200 ppm each of these two components. There is no indication of a possibly synergistic interaction of these two components in the quantities indicated.

The EP-A-0 374 461 , according to the US-A-5,004,478 , describes gasoline fuels, additized with a mixture of 50 to 1000 ppm of nitrogen-containing detergent additive and 50 to 5000 ppm of a carrier oil mixture of a) a polyalkylene oxide based on propylene oxide and / or butylene oxide with a molecular weight of at least 500, with aliphatic or b) esters of monocarboxylic acids or polycarboxylic acids and alkanols or polyols, these esters having a minimum viscosity of 2 cm ² / s at 100 ° C. On a synergistic interaction of detergent additive and polyether component is also not referenced in this document.

The EP-A-0 706 553 describes fuel additive compositions comprising a hydrocarbon-substituted amine having a molecular weight of about 700 to 2,000, a polyolefin polymer of a C ₂ -C ₆ monoolefin having a molecular weight of about 350 to 2,000, and a poly (oxyalkylene) monool having a terminal hydrocarbon group and an average molecular weight from about 500 to 5,000, wherein the terminal hydrocarbon group is a C ₁ -C ₃₀ hydrocarbyl group. Concrete examples of such polyether components are dodecylphenyl-initiated poly (oxy) butylenes having a molecular weight of about 1500, which are preferably used in combination with a polyisobutene amine having a molecular weight of 1300. Alkanol-initiated polyether compounds and their combined use with detergent additives are not described in this document.

The EP-A-0 887 400 describes gasoline blends supplemented with 50 to 70 ppm N-containing detergent having a molecular weight in the range of 700 to 3000 and 35 to 75 ppm of hydrocarbyl-terminated poly (oxyalkylene) monool having a molecular weight of 500 to 5000. Preferred hydrocarbyl end groups are C ₇ C ₃₀ alkylphenyl groups, in particular dodecylphenyl.

1. (i) einem Polymer eines C₂ - C₆-Monoolefins
2. (ii) einem Copolymer eines C₂ - C₆-Monoolefins
3. (iii) den entsprechenden hydrogenierten Polymeren oder Copolymeren
4. (iv) einem öllöslichen Poly(oxyalkylen)alkohol, Glykol oder Polyol oder einem Mono- oder Diether davon mit definierter Strukturformel und
5. (v) einem naphthenischen oder paraffinischen Öl mit einer Viskosität von 2 bis 15 cS bei 100 °C verwendet wird.

The US 5,006,130 describes additive combinations with intake valve cleaning action for gasoline fuels, wherein an additive mixture of (a) at least 2.5 ppm of an oil-soluble aliphatic alkylene polyamine having a molecular weight of 600-10,000 and (b) 75-125 ppm of a component selected from

1. (i) a polymer of a C ₂ -C ₆ monoolefin
2. (ii) a copolymer of a C ₂ -C ₆ monoolefin
3. (iii) the corresponding hydrogenated polymers or copolymers
4. (iv) an oil-soluble poly (oxyalkylene) alcohol, glycol or polyol or a mono- or diether thereof having a defined structural formula and
5. (v) a naphthenic or paraffinic oil having a viscosity of 2 to 15 cS at 100 ° C is used.

1. (i) eine Polyetheralkoholkomponente spezieller Struktur
2. (ii) eine Hydrocarbylphenolkomponente mit 1 bis 3 Hydrocarbylresten mit Molekulargewichten von 250 bis 6000 und gegebenenfalls
3. (iii) als dritte Komponente ein stickstoffhaltiges Dispergiermittel umfasst.

From the EP-A-0 878 532 For example, an additive combination for reducing intake valve deposits in internal combustion engines is known

1. (i) a polyether alcohol component of specific structure
2. (ii) a hydrocarbylphenol component having 1 to 3 hydrocarbyl radicals having molecular weights of 250 to 6,000 and optionally
3. (iii) as a third component comprises a nitrogen-containing dispersant.

1. a) wenigstens ein Detergensadditiv;
2. b) ein Trägerölgemisch, umfassend
   1. (i) wenigstens ein synthetisches Trägeröl und
   2. (ii) wenigstens ein mineralisches Trägeröl; und
3. c) gegebenenfalls weitere übliche Kraftstoffadditivkomponenten.
   Derartige Mischungen finden Verwendung als Kraftstoffadditivzusammensetzungen zur Verringerung der Einlassventilablagerungen in Verbrennungsmotoren.

The WO-A-01/85874 describes fuel additive compositions characterized by

1. a) at least one detergent additive;
2. b) a carrier oil mixture comprising
   1. (i) at least one synthetic carrier oil and
   2. (ii) at least one mineral carrier oil; and
3. c) optionally further customary fuel additive components.
   Such mixtures find use as fuel additive compositions to reduce intake valve deposits in internal combustion engines.

The WO-A-00/02978 describes fuel compositions for internal combustion engines, comprising a major amount of a liquid hydrocarbon fuel and a cleaning portion of at least one specific polypropoxylate additive, which may be additionally combined with at least one detergent additive.

However, the previously known additive packages require further optimization.

It was therefore an object to provide fuel additive packages for gasoline fuels, which are characterized by very good cleanliness effects in the intake system.

It has now been found, according to the invention, that by selecting defined mixtures of synthetic carrier oils and detergent additives it is possible to provide formulations for gasoline fuels which cooperate synergistically in a particularly advantageous manner and exhibit a particularly effective intake system-cleaning action.

• i) die Detergensadditivkomponente (A) wenigstens ein Polyalkenmonoamin ist, das mit einem Hydrocarbylrest mit einem zahlenmittleren Molekulargewicht von etwa 500 bis 1300 substituiert ist, und wobei die Detergensadditivkomponente (A) in dem Kraftstoff in einem Mengenanteil von etwa 30 bis 180 Gew.-ppm enthalten ist; und
• ii) die Trägerölkomponente (B) aus wenigstens einer Verbindung der folgenden allgemeinen Formel I besteht
  
          R-O-(A-O)_x-H     (I)
  
  worin

  R

  für eine geradkettige oder verzweigte C₆-C₁₈-Alkylgruppe steht;

  A

  für eine C₃- oder C₄-Alkylengruppe steht; und

  x

  für einen ganzzahligen Wert von 5 bis 35 steht;

  wobei die Trägerölkomponente (B) in dem Kraftstoff in einem Mengenanteil von etwa 10 bis 180 Gew.-ppm enthalten ist, als Ottokraftstoffzusatz zur Renigung des Motor- Einlasssystems.

The object of the invention is the use of a synergistic mixture consisting of a detergent additive component (A) and a synthetic carrier oil component (B), wherein:

• i) the detergent additive component (A) is at least one polyalkene monoamine substituted with a hydrocarbyl radical having a number average molecular weight of about 500 to 1300, and wherein the detergent additive component (A) is present in the fuel in a proportion of about 30 to 180 ppm by weight is included; and
• ii) the carrier oil component (B) consists of at least one compound of the following general formula I.
  
  RO- (AO) _x -H (I)
  
  wherein

  R

  is a straight or branched C ₆ -C ₁₈ alkyl group;

  A

  represents a C ₃ or C ₄ alkylene group; and

  x

  is an integer value of 5 to 35;

  wherein the carrier oil component (B) is contained in the fuel in an amount of about 10 to 180 ppm by weight, as a gasoline additive to the deterioration of the engine inlet system.

Preferably, fuels are provided, comprising component (A) in a proportion of 50 to 150 ppm by weight, in particular in a proportion of 70 to 130 ppm by weight; and fuels containing component (B) in a proportion of 20 to 150 ppm by weight, in particular in a proportion of 60 to 130 ppm by weight.

According to a further preferred variant, a polyisobuteneamine is used as component (A). Preferably, component (B) is a compound of formula I wherein R is a straight or branched C ₈ -C ₁₅ alkyl group; wherein A is butylene; and / or wherein x is an integer value of 16 to 25, in particular an integer value of 20 to 24. Particular preference is given to using as component (B) an isotridecanol butoxylate.

There now follows a detailed description of the invention.

1. Detergent Additive Component (A)

Fuel additive compositions preferred according to the present invention comprise as detergent additive component (component A) a detergent additive selected from polyalkene moamines and mixtures thereof. Examples of useful polyalkenamines are poly-C ₂ -C ₆ -alkeneamines and functional derivatives thereof, each containing a hydrocarbyl radical having a preferred Mn of about 500 to 1500, preferably about 600 to 1200, in particular about 700 to 1100 g. Suitable amines include, in addition to ammonia, mono- and di-C ₁ -C ₆ -alkylamines, such as mono- and dimethylamine, mono- and diethylamine, mono- and di-n-propylamine, mono- and di-n-butylamine, mono- and Di-sec-butylamine, mono- and di-n-pentylamine, mono- and di-2-pentylamine, mono- and di-n-hexylamine, etc. Also suitable are mono- or dialkylamines in which the alkyl radicals are optionally substituted by an or several, non-adjacent oxygen atoms are interrupted and may optionally also have hydroxyl groups. These include, for example, ethanolamine, 3-aminopropanol and 2- (2-aminoethoxy) ethanol.

Particularly suitable polyalkene monoamines or functional derivatives thereof according to the invention are in particular poly-C ₂ -C ₆ -alkeneamines, such as poly-C ₃ -C ₄ -alkeneamines, or functional derivatives thereof, for example compounds having a hydrocarbyl radical, prepared by polymerization of ethylene, Propene, 1- or 2-butene, i-butene, or mixtures thereof.

Examples of functional derivatives of the above additives are compounds which, for example in the amine part, carry one or more polar substituents, in particular hydroxyl groups.

Preferred additives which can be used according to the invention are polyalkene monoamines based on polypropene or of highly reactive (i.e., predominantly terminal double bonds) or conventional (i.e., predominantly intermediate double bonds) polybutene or polyisobutene.

Particularly suitable polyisobutenes are so-called "highly reactive" polyisobutenes, which are distinguished by a high content of terminal ethylenic double bonds. Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, in particular greater than 80 mol% and in particular greater than 85 mol%. Particular preference is given to polyisobutenes which have uniform polymer skeletons. Uniform polymer skeletons have, in particular, those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and more preferably at least 95% by weight, of isobutene units. Preferably, such highly reactive polyisobutenes have a number average molecular weight M _N in the range mentioned above. In addition, the highly reactive polyisobutenes may have a polydispersity of less than 1.9, such as less than 1.5. By polydispersity is meant the quotient of weight average molecular weight M _W divided by the number average molecular weight M _N.

Such additives based on highly reactive polyisobutene, which can be prepared from polyisobutene, which may contain up to 20% by weight of n-butene units, by hydroformylation and reductive amination with ammonia or monoamines, are known in particular from US Pat EP-A-0 244 616 or EP-A-0 578 323 known.

If one starts with the preparation of the additives of polybutene or polyisobutene with predominantly central double bonds (usually in the beta and gamma position), the preparation path is suitable by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. For amination, the same amines as described above can be used for the reductive amination of the hydroformylated highly reactive polyisobutene. Corresponding additives based on polypropene are especially in the WO 94/24231 described.

Further preferred monoamine-containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in US Pat DE-A 196 20 262 are described.

Particularly useful polyalkenamine-type detergent additives are sold by BASF AG, Ludwigshafen under the tradename Kerocom PIBA. These contain polyisobuteneamines dissolved in aliphatic C ₁₀ -C ₁₄ hydrocarbons and can be used as such in the additive packages according to the invention.

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 abgeleitete Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und
9. (i) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen;

The fuel additive mixtures used in the present invention may optionally contain other detergency (A) -type gasoline additives having valve seat wear-inhibiting action (hereinafter referred to as detergent additives) (which is not the subject of the present invention). This detergent additive has at least one hydrophobic hydrocarbon radical having a number average molecular weight (M _N ) of from 85 to 20,000 and at least one polar group selected from:

1. (a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;
2. (b) nitro groups, optionally in combination with hydroxyl groups;
3. (c) hydroxyl groups in combination with mono- or polyamino groups, wherein 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 moieties terminated by hydroxyl groups, mono- or polyamino groups wherein at least one nitrogen atom has basic properties or by carbamate groups;
7. (g) carboxylic acid ester groups;
8. (h) succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups; and
9. (i) moieties generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines;

The hydrophobic hydrocarbon radical in the above detergent additives, which provides sufficient solubility in the fuel, has a number average molecular weight (M _N ) of from 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5,000. As a typical hydrophobic hydrocarbon radical, especially in Compound with the polar groups (a), (c), (h) and (i), come the polypropenyl, polybutenyl and polyisobutenyl radical each having M _N = 300 to 5000, in particular 500 to 2500, especially 700 to 2300, into consideration.

As examples of the above groups of detergent additives, the following are mentioned:

Mono- or polyamino (a) -containing additives are preferably polyalkylene mono- or polyalkene polyamines based on polypropene or of highly reactive (ie predominantly terminal double bonds) or conventional (ie predominantly intermediate double bonds) polybutene or polyisobutene having M _n = 300 to 5000. Such Additives based on highly reactive polyisobutene, which are prepared from the polyisobutene, which may contain up to 20% by weight of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine in particular, are from the EP-A-244 616 known. If one proceeds in the preparation of the additives of polybutene or polyisobutene with predominantly central double bonds (usually in the beta and gamma position), the preparation route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. For amination can here the same Amines as above used for the reductive amination of the hydroformylated highly reactive polyisobutene. Corresponding additives based on polypropene are especially in the WO 94/24231 described.

Further preferred monoamino groups (a) containing additives 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 WO-A-97/03946 are described.

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

Nitro groups, optionally in combination with hydroxyl groups, (b) containing additives are preferably reaction products of polyisobutenes of the 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 WO-A-96/03367 and WO-A-96/03479 are described. These reaction products generally represent mixtures of pure nitropolyisobutanes (eg, α, β-dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (eg, α-nitro-β-hydroxypolyisobutane).

Hydroxyl groups in combination with mono- or polyamino groups (c) containing additives are in particular reaction products of polyisobutene epoxides, obtainable from preferably predominantly terminal double bonds having polyisobutene with M _N = 300 to 5000, with ammonia, mono- or polyamines, as described in particular EP-A-476485 are described.

Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives are preferably copolymers of C ₂ -C ₄₀ olefins with maleic anhydride having a total molecular weight of 500 to 20 000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines. Such additives are in particular from the EP-A-307,815 known. Such additives are primarily for preventing valve seat wear and can, as in the WO-A-87/01126 described, be used with advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.

Sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinsäurealkylesters, as described in particular in EP-A-639 632 is described. Such additives are primarily used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.

Polyoxy-C ₂ -C ₄ alkylene groupings (f) containing additives are preferably polyethers or polyetheramines, which by reaction of 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 EP-A-310 875 . EP-A-356 725 . EP-A-700 985 and U.S. Patent 4,877,416 described. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Carboxylic ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm ² / s at 100 ° C, as in particular DE-A-38 38 918 are described. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable long-chain representatives having, for example, 6 to 24 carbon atoms as ester alcohols or polyols. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.

Succinic anhydride derived groupings containing hydroxyl and / or amino and / or amido and / or imido groups (h) are preferably corresponding derivatives of polyisobutenyl succinic anhydride obtained by reacting conventional or highly reactive polyisobutene with M _n = 300 to 5000 with maleic anhydride are obtainable by thermal means or via the chlorinated polyisobutene. Of particular interest here are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such gasoline additives are particularly useful in U.S. Patent 4,849,572 described.

By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives 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 M _n = 300 to 5,000. Such "polyisobutene-Mannich bases" are particularly in the EP-A-831 141 described.

For a more detailed definition of the individual listed petrol additives, reference is made here expressly to the disclosures of the abovementioned prior art documents.

2. Carrier oil component (B)

R

für eine geradkettige oder verzweigte C₆-C₁₈-, insbesondere eine C₈-C₁₅-Alkylgruppe steht;

A

für eine C₃- oder C₄-Alkylengruppe steht; und

x

für einen ganzzahligen Wert von 5 bis 35, wie z. B. 16 bis 25 oder 20 bis 24 steht.

The carrier oil component (B) according to the invention consists of at least one compound of the following general formula I.

RO- (AO) _x -H (I)

wherein

R

is a straight-chain or branched C ₆ -C ₁₈ -, in particular a C ₈ -C ₁₅ -alkyl group;

A

represents a C ₃ or C ₄ alkylene group; and

x

for an integer value of 5 to 35, such. B. 16 to 25 or 20 to 24 stands.

Examples of suitable radicals R are n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl and n-octadecyl and the mono- or polysubstituted analogs thereof, such as. Iso-tridecyl, and mixtures of such isomers.

Examples of suitable radicals A are propylene and 1- or 2-butylene and iso-butylene.

Examples of suitable polyethers (B) are preferably polyoxy-C ₂ -C ₄ -alkylene group-containing compounds obtained by reacting C ₆ -C ₁₈ -alkanols with 5 to 35 mol of C ₃ -C ₄ -alkylene oxide are available per hydroxyl group. Such products are used in particular EP-A-0 310 875 . EP-A-0 356 725 . EP-A-0 700 985 and US-A-4,877,416 described. Typical examples of this are Tridecanol- or Isotridecanolbutoxylate and corresponding isomer mixtures thereof

3. Other additives

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

The components or additives can be added to the gasoline fuel individually or as a previously prepared concentrate (additive package) together with the high molecular weight polyalkene according to the invention.

The said (A) different detergent additives with the polar groups (a) to (i) are added to the gasoline usually 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 customary amounts.

4. Petrol

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 Ed. 1990, Vol. A16, p. 719 et seq.

For example, use in a gasoline having an aromatic content of at most 42% by volume and a sulfur content of at most 150 ppm by weight is possible.

The aromatic content of the gasoline is, for example, from 30 to 42% by volume, in particular from 32 to 40% by volume.

The sulfur content of the gasoline is for example 5 to 150 ppm by weight, in particular 10 to 100 ppm by weight.

The gasoline, for example, has an olefin content of 6 to 21% by volume, in particular 7 to 18% by volume.

The gasoline may, for example, have a benzene content of from 0.5 to 1.0% by volume, in particular from 0.6 to 0.9% by volume.

The gasoline, for example, has an oxygen content of 1.0 to 2.7 wt .-%, in particular from 1.2 to 2.0 wt .-%, on.

In particular, such gasoline fuels may be mentioned by way of example, which at the same time has an aromatics content of not more than 38% by volume, an olefin content of not more than 21% by volume, a sulfur content of not more than 50 ppm by weight, a benzene content of not more than 1.0% by volume. and have an oxygen content of 1.0 to 2.7% by weight.

The content of alcohols and ethers in gasoline is usually relatively low. Typical maximum contents for methanol are 3% by volume, for ethanol 5% by volume, for isopropanol 10% by volume, for tert-butanol 7% by volume, for isobutanol 10% by volume and for ethers 5 or more C atoms in the molecule 15 vol .-%.

The summer vapor pressure of the gasoline is usually not more than 70 kPa, in particular 60 kPa (each at 37 ° C).

The ROZ of the gasoline is usually 90 to 100. A common range for the corresponding MOZ is 80 to 90.

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

The invention will now be explained in more detail with reference to the following embodiment.

example

A mixture of equal parts of the detergent additive (PIBA = polyisobutene monoamine (M _w = 1000)) and iso-tridecanol, etherified with 22 moles of butylene oxide, forth and thus additizes a commercially available base fuel according to DIN EN 228 in different Amounts. For comparison, the same fuel is only additized with PIBA.

With these fuels, as well as with unadditized fuel, a Mercedes Benz M 102 E engine test is performed to determine intake system deposits (CEC F-05-A-93). The results are summarized in the following table.

The test results show that the additive mixtures according to the invention, despite a lower detergent additive content, have a significantly better intake system-cleaning action. Table 1 Test no. additive Dosage ³⁾ mg / kg Valve deposit (mg (valve) Average 1 2 3 4 1 --- 0 293 593 296 338 380 2 PIBA ¹⁾ 200 42 11 108 99 65 3 PIBA ¹⁾ / polyether ²⁾ 100/100 5 25 100 52 46 4 PIBA ¹⁾ / polyether ²⁾ 134/134 10 8th 48 7 18 ¹⁾ PIBA = polyisobuteneamine (M _w = 1000)
²⁾ polyether = iso-tridecanol, etherified with 22 1-butylene oxide units
³⁾ dosage in each case based on pure substance

Claims (11)

1. The use of a synergistic additive combination, consisting of a synergistic mixture of a detergent additive component (A) and a synthetic carrier oil component (B) as a gasoline fuel additive for cleaning the engine intake system,

   i) the detergent additive component (A) being at least one polyalkene monoamine which is substituted by a hydrocarbyl radical having a number average molecular weight of from about 500 to 1300,
   the detergent additive component (A) being present in the fuel in an amount of from about 30 to 180 ppm by weight; and

   ii) the carrier oil component (B) consisting of at least one compound of the following formula I
   
           R-O-(A-O)_x-H     (I)
   
   where

   R is a straight-chain or branched C₆-C₁₈-alkyl group;

   A is a C₄-alkylene group; and

   x is an integer from 5 to 35;

   the carrier oil component (B) being present in the fuel in an amount of from about 10 to 180 ppm by weight.
2. The use according to claim 1, comprising component (A) in an amount of from 50 to 150 ppm by weight.
3. The use according to either of the preceding claims, comprising component (A) in an amount of from 70 to 130 ppm by weight.
4. The use according to any of the preceding claims, comprising component (B) in an amount of from 20 to 150 ppm by weight.
5. The use according to any of the preceding claims, comprising component (B) in an amount of from 60 to 130 ppm by weight.
6. The use according to any of the preceding claims, component (A) being a polyisobutenamine.
7. The use according to any of the preceding claims, component (B) being a compound of the formula I, where R is a straight-chain or branched C₈-C₁₅-alkyl group.
8. The use according to any of the preceding claims, component (B) being a compound of the formula I, where A is butylene.
9. The use according to any of the preceding claims, component (B) being a compound of the formula I, where x is an integer from 16 to 25.
10. The use according to any of the preceding claims, component (B) being a compound of the formula I, where x is an integer from 20 to 24.
11. The use according to any of the preceding claims, component (B) being a tridecanol butoxylate.