KR20130095660A - Low-molecular weight polyisobutyl-substituted amines as dispersant boosters - Google Patents

Abstract

(A) a polyisobutyl nitrogen-containing dispersant having a M _N of polyisobutyl group of 650 to 1800 Daltons, (B) a carrier oil substantially free of nitrogen, and (C) a M _N of polyisobutyl group of 200 to 650 Daltons A fuel additive composition comprising a phosphorus polyisobutyl-based dispersant booster, provided that the difference between M _N of the polyisobutyl group of component (A) and M _N of the polyisobutyl group of component (C) exceeds 100 Daltons Fuel additive composition. Component (C) is particularly useful as an intake valve cleaning booster in a port fuel injection internal combustion engine operated with gasoline.

Description

LOW-MOLECULAR WEIGHT POLYISOBUTYL-SUBSTITUTED AMINES AS DISPERSANT BOOSTERS} Low molecular weight polyisobutyl-substituted amines as dispersant boosters

The present invention relates to (A) Mannich adducts of polyisobutyl monoamines, polyisobutyl polyamines, polyisobutylphenols, aldehydes and monoamines, and Mannich adducts of polyisobutylphenols, aldehydes and polyamines. Selected nitrogen-containing dispersants, (B) substantially nitrogen free carrier oils selected from synthetic and mineral carrier oils, and (C) low molecular weight, polyisobutyl monoamines, polyisobutyl polyamines, polyisobutylphenols, A novel fuel additive composition comprising a Mannich adduct of aldehydes and monoamines and a dispersant booster selected from Mannich adducts of polyisobutylphenols, aldehydes and polyamines. The invention also relates to a gasoline fuel composition comprising a small amount of said fuel additive composition. The present invention further relates to the use of such low molecular weight polyisobutyl-substituted amines as dispersant boosters in gasoline operated internal combustion engines containing the dispersant and the carrier oil.

The carburettor and inlet system of an automotive engine, and also the injection system for fuel distribution, are contaminated by dust particles from the air, unburned hydrocarbon residues and crankcase ventilation from the combustion chamber, and the recirculation of exhaust gases passed into the intake system. This results in an increase in load.

This residue shifts the air: fuel ratio during idling and in the lower partial load zones, resulting in a more concentrated mixture and incomplete combustion, which in turn leads to an unburned or partially burned hydrocarbon content in the exhaust gas. Increase and gasoline consumption rises.

These disadvantages are known to be addressed through the use of fuel additives for cleaning valves and carburettors or injection systems of Otto engines (see, for example, M. Rossenbeck in "Katalysatoren, Tenside, Mineraloeladditive ", edited by J. Falbe, U. Hasserodt, page 223, G. Thieme Verlag, Stuttgart 1978).

For trouble-free operation, modern auto engines require automotive fuels with a complex set of characteristics that can only be guaranteed if only appropriate gasoline additives are used. Such fuels generally consist of a complex mixture of compounds and are characterized by physical parameters.

Fuel additives are used to avoid the formation of deposits in the intake system and intake valves of the engine (keep-clean effect). On the other hand, fuel additives can be used to remove deposits that have already formed in the valves and intake systems (clean-up effect).

Aliphatic primary, secondary and tertiary monoamines having C ₁ -C ₂₀ -alkyl residues or C ₃ -C ₂₀ -cycloalkyl residues are according to WO 04/050806 as dispersant additives in gasoline fuels, preferably Mannich type. It is known to be combined with dispersant additives. The monoamines are polyisobutyl monoamines or polyisobutyl polyamines based on polyisobutenes having a number average molecular weight of 600 to 5000 in gasoline fuels, and polyether carrier oils such as tridecanol butoxylate Or isotridecanol butoxylate. The use of such monoamines reduces the odor of the injector nozzles in a direct injection spark ignition engine.

WO 03/076554 describes hydrocarbyl moieties having a number average molecular weight in the range of 140 to 255 to reduce the odor of injector nozzles in such engines for the purpose of "cleaning" or "cleaning" of direct injection spark ignition engines. The use of hydrocarbyl amines is described. In fuel D of the example of WO 03/076554, the gasoline fuel is " polyisobutyl monoamine (PIBA), polyether carrier fluid and a polyisobutylene (PIB) chain having a number average molecular weight (M _N ) of approximately 1000; "Addition of 50 ppmw dodecylamine into 645 ppmw of base fuel of a commercial additive package containing antioxidant (eg BASF AG)." Fuel D was subjected to a cleaning test that measured the average injector diameter reduction after running a direct injection spark ignition engine using this fuel.

WO 90/10051 discloses (1) long chain primary amines which typically present C ₆ -C ₄₀ aliphatic radicals as substituents, for example decyl amine, dodecyl amine (lauryl amine), or tetradecyl amine, hexadecyl Tallow amines containing amines, octadecyl amines and octadecenyl amines (oleyl amines), (2) fuel dispersants selected from polyalkylamines (e.g. polyisobutyl amines) and Mannich bases, and ( 3) A gasoline fuel composition containing a suction valve deposit control additive formulation comprising with a fluidizer oil such as purified naphthenic lubricants or polyolefins (eg polypropylene or polybutylene).

US 2007/0094922 A1 relates to polyalkene amines with improved application properties, such as polyisobutyl monoamines, for use as additives in fuel or lubricant compositions. Suitable polyisobutyl monoamines are highly reactive polys available from BASF AG under the trade names Glissopal®, in particular "Glissopal 1000 (Mn = 1000), Glissopal V 33 (Mn = 550) and Glissopal 2300 (Mn = 2300) and mixtures thereof". Derived from isobutene. Polyalkene amines such as polyisobutyl monoamines disclosed in US 2007/0094922 A1 can be used with mineral carrier oils or synthetic carrier oils.

US 3,898,056 discloses a mixture of high molecular weight hydrocarbyl amines and low molecular weight hydrocarbyl amines for use in the field of automotive fuel additives. High molecular weight hydrocarbyl amines contain hydrocarbyl groups having a molecular weight of about 1900 to 5000; Such amines can be readily prepared by reacting the corresponding hydrocarbyl halides with monoamines or polyamines. Low molecular weight hydrocarbyl amines contain hydrocarbyl groups having a molecular weight of about 300 to 600; Such amines can also be readily prepared by reacting the corresponding hydrocarbyl halides with monoamines or polyamines. Examples of such high molecular weight hydrocarbyl amines and low molecular weight hydrocarbyl amines are prepared from the corresponding polyisobutylenes. High molecular weight hydrocarbyl amines and low molecular weight hydrocarbyl amines disclosed in US Pat. No. 3,898,056 can be used with fuel soluble carrier oils such as nonvolatile mineral lubricants or polyalkoxy polyols.

The interaction between gasoline fuels and appropriate fuel additives in the fuel composition may still be unsatisfactory in terms of their intake valve cleaning performance. It is therefore an object of the present invention to provide an improved fuel additive formulation with efficient control of deposits formed in the engine, in particular with improved intake valve cleaning performance.

The following fuel additive compositions have been found to significantly improve the intake valve cleaning performance of gasoline fuel. The fuel additive composition is:

(A) Mannich adduct of polyisobutyl monoamine, polyisobutyl polyamine, polyisobutylphenol, aldehyde and monoamine, wherein the number average molecular weight M _N of the polyisobutyl group is 650-1800 Daltons, respectively, And one or more nitrogen-containing dispersants selected from Mannich adducts of polyisobutylphenol, aldehydes and polyamines,

(B) at least one carrier oil, substantially free of nitrogen, selected from synthetic and mineral carrier oils, and

(C) polyisobutyl monoamine, polyisobutyl polyamine, mannich adduct of polyisobutylphenol, aldehyde and monoamine, and polyiso, wherein the number average molecular weight M _N of the polyisobutyl group is 200 to 650 Daltons, respectively. One or more dispersant boosters selected from Mannich adducts of butylphenol, aldehydes and polyamines

Including,

Provided that the difference between M _N of the polyisobutyl group of component (A) and M _N of the polyisobutyl group of component (C) is greater than 100 Daltons, preferably greater than 250 Daltons, more preferably 100 In the range from greater than 900 to Dalton, most preferably in the range from greater than 250 to 600 Dalton. Therefore, the fuel additive composition is the first protective object of the present invention.

A second protected object of the present invention is a fuel composition comprising a large amount of liquid fuel in the gasoline boiling range and a small amount of the fuel additive composition.

The third protection object of the present invention is (A) polyisobutyl monoamine, polyisobutyl polyamine, polyisobutylphenol, aldehyde and monoamine, wherein the number average molecular weight M _N of the polyisobutyl group is 650 to 1800 Dalton, respectively. At least one nitrogen-containing dispersant selected from the Mannich adducts and the Mannich adducts of polyisobutylphenol, aldehydes and polyamines, and (B) at least one carrier oil substantially free of nitrogen, selected from synthetic and mineral carrier oils. Polyisobutyl, wherein the number average molecular weight M _N of the polyisobutyl group (C) as described in claim 1 as a dispersant booster in an internal combustion engine operated on a liquid fuel in a gasoline boiling range containing a small amount is 200 to 650 daltons each; Mannich adducts of monoamines, polyisobutyl polyamines, polyisobutylphenols, aldehydes and monoamines, or polyisobutylphenols, Only of formaldehyde and a Mannich polyamine added is the use of water.

Nitrogen Dispersant  (Component A)

The polyisobutenes suitable for preparing the polyisobutyl monoamines, polyisobutyl polyamines and polyisobutyl-substituted Mannich adducts used in the present invention are at least about 20 mol%, preferably at least 50 mol%, more preferably Preferably polyisobutene comprising at least 70 mol%, most preferably at least 80 mol% of more reactive methylvinylidene isomers (ie having terminal vinylidene double bonds). Suitable polyisobutenes include those made using BF ₃ catalysts. The preparation of such polyisobutenes in which methylvinylidene isomers are included in high percentages in the total composition is described, for example, in US Pat. No. 4,152,499 and US Pat. Starting from a technical C ₄ stream containing ten, such as raffinate I.

Examples of suitable polyisobutenes with a high methylvinylidene content are products, such as those of British Petroleum, Ultravis® 30 (number average molecular weight of about 1300 and polyvinylidene content of about 74 mol%). Isobutene), and Ultravis®10 (polyisobutene of 950 molecular weight with a methylvinylidene content of about 76 mol%). Another example of a suitable polyisobutene having a number average molecular weight of about 1000 and a high methylvinylidene content is Glissopal®1000 (available from BASF SE).

In most cases, the polyisobutene precursor is not a pure single product but rather a mixture of compounds having a number average molecular weight in the above range. In general, the molecular weight distribution range will be a relatively narrow range with a maximum close to the indicated molecular weight.

The amine component of each polyisobutyl monoamine or polyisobutyl polyamine can be derived from ammonia, monoamine or polyamine.

Monoamine or polyamine components include amines having 1 to about 12 amine nitrogen atoms and 1 to 40 carbon atoms. The carbon: nitrogen ratio may be about 1: 1 to about 10: 1. In general, monoamines will contain 1 to about 40 carbon atoms and polyamines will contain 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms.

The amine component can be a pure single product or a mixture of compounds with large amounts of the selected amine.

If the amine component is a polyamine, it may preferably be a polyalkylene polyamine including an alkylene diamine. Preferably, the alkylene group will contain 2 to 6 carbon atoms, more preferably 2, 3 or 4 carbon atoms. Examples of such polyamines include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine. Preferred polyamines are ethylene diamine and diethylene triamine.

Particularly preferred polyisobutyl polyamines include polyisobutyl ethylene diamine and polyisobutyl diethylene triamine. Polyisobutyl groups are substantially saturated.

The polyisobutyl monoamines or polyisobutyl polyamines used in the fuel additive compositions of the present invention are prepared by conventional procedures known in the art, in particular of the corresponding highly reactive polyisobutenes as described in EP-A 0 244 616. Prepared by hydroformylation and subsequent reductive amination. In more detail, highly reactive polyisobutenes having a high content of terminal vinylidene double bonds, especially terminal vinylidene double bonds of at least 70 mol%, more preferably at least 80 mol%, are hydroformylation catalysts, for example In the presence of a suitable rhodium or cobalt catalyst, it is preferably reacted with carbon monoxide and hydrogen in an inert solvent such as a hydrocarbon solvent, typically at a temperature in the range from 80 to 200 ° C. and a CO / H ₂ -pressure of up to 600 bar. The resulting oxo intermediate is then typically in the presence of hydrogen, a suitable nitrogen compound, a suitable catalyst such as Raney nickel or Raney cobalt, preferably in an inert solvent such as a hydrocarbon solvent or an alcohol solvent, typically from 80 to It undergoes a reductive amination reaction at a temperature in the range of 200 ° C. and H ₂ -pressure of 80 to 300 bar.

The amine portion of the molecule may have one or more substituents. Thus, the carbon and / or especially nitrogen atoms of the amines are hydrocarbyl groups having 1 to about 10 carbon atoms, acyl groups having 2 to about 10 carbon atoms, and monoketo, monohydroxy, mononitro, mono Cyano, lower alkyl and lower alkoxy derivatives thereof. As used herein, "lower" means a group containing from 1 to about 6 carbon atoms. One or more hydrogen atoms on one of the basic nitrogen atoms of the polyamine may not be substituted such that one or more of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen atom.

The polyamines used within the scope of the invention as amine components for polyisobutyl polyamines may be polyalkylene polyamines, which include substituted polyamines such as alkyl and hydroxyalkyl-substituted polyalkylene polyamines. do. Among the polyalkylene polyamines, mention may be made of polyalkylene polyamines, in particular C ₂ -C ₃ alkylene polyamines, containing 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms. Preferably, the alkylene group contains 2 to 6 carbon atoms and preferably there are 2 to 3 carbon atoms between the nitrogen atoms. Such groups include ethylene, 1,2-propylene, 2,2-dimethylpropylene, trimethylene, 1,3- (2-hydroxy) -propylene.

Examples of such polyamines are ethylene diamine, diethylene triamine, di (trimethylene) triamine, 1,2-propylene diamine, 1,3-propylene diamine, dipropylene triamine, triethylene tetraamine, tripropylene tetraamine, Tetraethylene pentamine, pentaethylene hexamine, hexamethylene diamine, and 3- (N, N-dimethylamino) propyl-amine. Such amines encompass isomers such as branched polyamines and the aforementioned substituted polyamines, including hydroxy- and hydrocarbyl-substituted polyamines.

The amine component for polyisobutyl monoamine or polyisobutyl polyamine can also be derived from heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocycle is one containing oxygen and / or nitrogen It includes the above 5 to 6 membered ring. Such heterocyclic rings may be saturated or unsaturated and substituted with the groups defined above.

Examples of heterocyclic compounds include 2-methylpiperazine, N- (2-hydroxyethyl) -piperazine, 1,2-bis- (N-piperazinyl) ethane, N, N'-bis (N- Piperazinyl) -piperazine, 2-methylimidazoline, 3-aminopiperidine, 3-aminopyridine, N- (3-amino-propyl) -morpholine, N- (beta-aminoethyl) piperazine , N- (betaaminoethyl) piperidine, 3-amino-N-ethylpiperidine, N- (betaaminoethyl) morpholine, N, N'-di (beta-aminoethyl) -piperazine, N , N'-di (beta-aminoethyl) imidazolidone-2, 1,3-dimethyl-5 (beta-amino-ethyl) hexahydrotriazine, N- (betaaminoethyl) -hexahydrotriazine, 5- (beta-aminoethyl) -1,3,5-dioxazine may be mentioned.

Alternatively, the amine component for the polyisobutyl monoamine can be derived from a monoamine having the formula HNR ¹ R ² , wherein R ¹ and R ² are independently hydrogen and hydrocarbyl of 1 to about 20 carbon atoms. And R ¹ and R ² can be taken together to form one or more five or six membered rings containing up to about 20 carbon atoms. Preferably, R ¹ is hydrogen and R ² is a hydrocarbyl group having 1 to about 10 carbon atoms. More preferably, R ¹ and R ² are hydrogen. Hydrocarbyl groups can be straight or branched and can be aliphatic, cycloaliphatic, aromatic or combinations thereof. Hydrocarbyl groups may also contain one or more oxygen atoms.

Typical primary amines include N-methylamine, N-ethylamine, Nn-propyl-amine, N-isopropylamine, Nn-butylamine, N-isobutylamine, N-sec-butylamine, N-tert-butyl Amine, Nn-pentylamine, N-cyclopentylamine, Nn-hexylamine, N-cyclohexyl-amine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N-benzyl -Amine, N- (2-phenylethyl) amine, 2-aminoethanol, 3-amino-1-propanol, 2- (2-amino-ethoxy) ethanol, N- (2-methoxyethyl) amine, N -(2-ethoxyethyl) amine, etc. are illustrated. Preferred primary amines are N-methylamine, N-ethylamine and N-n-propylamine.

Typical secondary amines are N, N-dimethylamine, N, N-diethylamine, N, N-di-n-propylamine, N, N-diisopropylamine, N, N-di-n-butylamine , N, N-di-sec-butylamine, N, N-di-n-pentylamine, N, N-di-n-hexylamine, N, N-dicyclohexylamine, N, N-dioctylamine , N-ethyl-N-methylamine, N-methyl-Nn-propylamine, Nn-butyl-N-methylamine, N-methyl-N-octylamine, N-ethyl-N-isopropylamine, N-ethyl -N-octylamine, N, N-di- (2-hydroxy-ethyl) amine, N, N-di (3-hydroxypropyl) amine, N, N-di (ethoxyethyl) amine, N, N-di- (propoxyethyl) amine, and the like. Preferred secondary amines are N, N-dimethylamine, N, N-diethylamine and N, N-di-n-propylamine.

Cyclic secondary amines can also be used to form the polyisobutyl monoamines or polyisobutyl polyamines used in the present invention. In such cyclic compounds, R ¹ and R ² of the above formula together form one or more five or six membered rings containing up to about 20 carbon atoms. Rings containing amine nitrogen atoms are generally saturated but may be fused to one or more saturated or unsaturated rings. The ring may be substituted with a hydrocarbyl group of 1 to about 10 carbon atoms and may contain one or more oxygen atoms.

Suitable cyclic secondary amines include piperidine, 4-methylpiperidine, pyrrolidine, morpholine, 2,6-dimethylmorpholine, and the like.

The number average molecular weight M _N of the polyisobutyl groups in the polyisobutyl monoamine, polyisobutyl polyamine and polyisobutyl-substituted Mannich adduct used in the present invention as the nitrogen-containing dispersant component (A) is 650 to 1800 Daltons. , Preferably 700 to 1500 Daltons, most preferably 750 to 1300 Daltons. As already mentioned for polyisobutene precursors, polyisobutyl monoamines, polyisobutyl polyamines and polyisobutyl-substituted Mannich adducts are mostly not pure single products but rather have a number average molecular weight as indicated above. Mixture of compounds. In general, the molecular weight distribution range will be a relatively narrow range with a maximum close to the stated molecular weight.

In one particularly preferred embodiment, the dispersant component (A) is a polyisobutyl mono having a number average molecular weight M _N of polyisobutyl groups of 650 to 1800 Daltons, preferably 700 to 1500 Daltons, most preferably 750 to 1300 Daltons Amine. Said polyisobutyl monoamine is preferably based on ammonia and / or preferably prepared by hydroformylation and subsequent reductive amination of the corresponding highly reactive polyisobutene as described in EP-A 0 244 616. do. In more detail, highly reactive polyisobutenes having a high content of terminal vinylidene double bonds, especially terminal vinylidene double bonds of at least 70 mol%, more preferably at least 80 mol%, are hydroformylation catalysts, for example , In the presence of a suitable rhodium or cobalt catalyst, preferably in an inert solvent such as a hydrocarbon solvent, typically with carbon monoxide and hydrogen at temperatures ranging from 80 to 200 ° C. and CO / H ₂ -pressure up to 600 bar. The oxo intermediates obtained are then in the presence of hydrogen, a suitable nitrogen compound, a suitable catalyst, such as lyny nickel or lyny cobalt, preferably in an inert solvent such as a hydrocarbon solvent or an alcohol solvent, typically in the range of 80 to 200 ° C. Undergo a reductive amination reaction at a temperature of and a H ₂ -pressure of 80 to 300 bar.

Mannich adducts suitable as component (A) of the present invention are (i) polyisobutyl in the aromatic ring system, preferably having a number average molecular weight M _N of from 650 to 1800 Daltons derived from the highly reactive polyisobutene as defined above In addition to substituents, one or more, for example one, two or three C ₁ to C ₇ alkyl substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl 1 to 2 moles of one or more polyisobutyl phenols, which may have n-pentyl or n-hexyl, (ii) 1 to 3 moles of one or more C ₁ to C ₆ aldehydes such as formaldehyde, acetaldehyde, and Propionaldehyde (which may be used in the form of oligomers or polymers, such as paraformaldehyde) and (iii) one to three moles of one or more primary or secondary amines of the formula HNR ³ R ⁴ , wherein R ³ is hydrogen, C ₁ To C ₂₀ alkyl residues or in C ₃ If C ₂₀ represents a cycloalkyl residue, R ⁴ is C ₁ to C ₂₀ alkyl residue or a C ₃ to represent a C ₂₀ cycloalkyl residue, two residues R ³ and R ⁴ form a ring system together with the nitrogen atom to which they are attached And / or may be independently of each other interrupted by one or more oxygen atoms and / or imino groups of the formula -NR ^5- (R ⁵ represents hydrogen or a C ₁ to C ₄ alkyl group), and / or R ⁴ is Can be terminated with a second -NH ₂ group). Such Mannich adducts are known in the art, for example in WO 04/050806.

Examples of straight and branched chain primary amines of the formula HNR ³ R ⁴ include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine , n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, 3-propylheptylamine, n-decylamine, n-undecylamine, n Dodecylamine, n-tridecylamine, iso-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nona Decylamine and n-eicosylamine.

Examples of linear, branched and cyclic secondary amines of the formula HNR ³ R ⁴ are dimethylamine, diethylamine, di n-propylamine, di-iso-propylamine, di-n-butylamine, di-iso- Butylamine, di-sec-butylamine, di-tert-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di- (2- Ethylhexyl) amine, di-n-nonylamine, di- (3-propylheptyl) amine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, di-n-tri Decylamine, di-iso-tridecylamine, di-n-tetradecylamine, di-n-pentadecylamine, di-n-hexadecylamine, di-n-heptadecylamine, di-n-octadecylamine , Di-n-nonadecylamine, di-n-eicosylamine, cyclooctylamine and cyclodecylamine.

Examples of amines of formula HNR ³ R ⁴ which may be interrupted by an imino group of formula -NR ⁵ -and / or terminated with a second -NH ₂ group are N- (3,3-dimethylamino) propylamine, 1,2 Ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

Typical examples of Mannich adducts suitable as component (A) include (i) one mole of 4-polyisobutylphenol (M _N = 1000 of polyisobutyl groups) and (ii) one mole of paraformaldehyde and ( iii) the reaction product of 1 mole of dimethylamine or di-n-butylamine or di (2-ethylhexyl) amine. Further typical examples of Mannich adducts suitable as component (A) are (i) 2 moles of 4-polyisobutylphenol (M _N = 1000 of polyisobutyl groups) and (ii) 2 moles of paraformaldehyde And (iii) 1 mole of methylamine or n-butylamine or 2-ethylhexylamine or 3- (N, N-dimethylamino) propylamine.

carrier  Oil (Component B)

The fuel soluble, nonvolatile carrier oil of component (B) is used as an essential component of the fuel additive composition of the present invention to achieve the desired improvement in intake valve cleaning performance. Carrier oils are chemically inert hydrocarbon soluble liquid vehicles. The carrier oil of component (B) can be a synthetic oil or a mineral oil; For the present invention, it is understood that the refined petroleum oil is also a mineral oil.

Such carrier oils (also called carrier fluids) are believed to act as carriers for fuel additives and to help remove deposits and retard their growth. Carrier oils (B) may also exhibit synergistic effects in deposit control and deposit removal properties when used with components (A) and (C) of the fuel additive compositions of the present invention.

The carrier oil of component (B) is typically used in an amount in the range of about 50 to about 2,000 ppm by weight of gasoline fuel, preferably 100 to 800 ppm by weight of gasoline fuel. Preferably, the ratio of carrier oil (B) to nitrogen-containing dispersant (A) in the gasoline fuel as well as in the fuel additive composition is in the range from 0.5: 1 to 10: 1, typically from 1: 1 to 4: 1.

When used in fuel additive compositions or fuel additive concentrates, for example in the fuel additive compositions of the present invention, the carrier oil will generally be present in an amount in the range of about 10 to about 60% by weight, preferably 20 to 40% by weight ( Taking into account the amounts of all components in the composition or concentrate, including possible solvents).

Examples of suitable mineral carrier oils are in particular aromatic and paraffinic hydrocarbons and alkoxyalkanols as well as those of the viscosity class solvent neutrals (SN) 500 to 2000. Another useful mineral carrier oil is a fraction known as “hydrocrack oil”, which is a purified mineral oil (boiling point of approximately 360 to 500 ° C .; isomerized, paraffinic and catalytically hydrogenated under high pressure). Obtainable from mineral oil).

Examples of synthetic carrier oils that may be used for the present invention are 400 having a number average molecular weight of 400 based on poly-alpha-olefins or poly-internal-olefins, in particular polybutene or polyisobutene (hydrogenated or nonhydrogenated) To 1800 olefin polymers. Further examples of suitable synthetic carrier oils are carboxylic acids of polyesters, polyalkoxylates, polyethers, alkylphenol-initiated polyethers, and long chain alkanols.

Examples of suitable polyethers which may be used in the present invention are compounds containing polyoxy-C ₂ -C ₄ -alkylene groups, especially polyoxy-C ₃ -C ₄ -alkylene groups, which are C ₁ -C ₃₀ -Alkanols, C ₂ -C ₆₀ -alkanediols, C ₁ -C ₃₀ -alkylcyclohexanol or C ₁ -C ₃₀ -alkylphenols containing from 1 to 30 moles of ethylene oxide and / or propylene oxide per hydroxyl group and And / or butylene oxide, in particular 1 to 30 moles of propylene oxide and / or butylene oxide per hydroxyl group. Compounds of this type are described, for example, in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.

Typical examples of suitable polyethers are tridecanol butoxylate, isotridecanol butoxylate, isononylphenol butoxylate, polyisobutenol butoxylate and polyisobutenol propoxylate.

Hydrocarbyl-terminated poly (oxyalkylene) polymers that can be used as component (B) in the present invention are monohydroxy compounds, ie alcohols, often monohydroxy polyethers, or polyalkylene glycol monohydrocarbylethers. , Or “capped” poly (oxyalkylene).

Hydrocarbyl-terminated poly (oxyalkylene) alcohols may be prepared by addition of lower alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, or pentylene oxide, to the hydroxy compound under polymerization conditions. Methods and properties of such polymers are described in US Pat. Nos. 2,841,479 and 2,782,240 and Kirk-Othmer's "Encyclopedia of Chemical Technology", 2nd Ed. Volume 19, p. 507. In the polymerization reaction, a single kind of alkylene oxide, for example propylene oxide, can be used, in which case the product is a homopolymer, for example poly (oxyalkylene) propanol. However, copolymers are equally satisfactory, and random copolymers are readily prepared by contacting a hydroxyl containing compound with a mixture of alkylene oxides, such as a mixture of propylene oxide and butylene oxide. Block copolymers of oxyalkylene units also provide satisfactory poly (oxyalkylene) copolymers for the practice of the present invention. Random polymers are more easily prepared when the reactivity of the oxides is relatively the same. In certain cases, when ethylene oxide is copolymerized with other oxides, higher reaction rates of ethylene oxide make it difficult to produce random copolymers. In either case, block copolymers can be prepared. Block copolymers are prepared by subjecting a hydroxyl containing compound to the first one alkylene oxide followed by another alkylene oxide in any order or repeatedly under polymerization conditions. Certain block copolymers are represented by polymers prepared by polymerizing propylene oxide on suitable monohydroxy compounds to form poly (oxypropylene) alcohols and then polymerizing butylene oxide on poly (oxyalkylene) alcohols.

In general, poly (oxyalkylene) polymers are mixtures of compounds having different polymer chain lengths. However, the properties of such polymers are very similar to those of polymers represented by average composition and molecular weight.

Examples of carboxylic acid esters of long chain alkanols are esters of long-chain alkanols or polyhydric alcohols with mono-, di- and tri-carboxylic acids, for example those described in DE-A 38 38 918. Suitable mono-, di- and tri-carboxylic acids are aliphatic or aromatic carboxylic acids. Suitable alkanols and polyhydric alcohols contain 6 to 24 carbon atoms. Typical examples of such esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, for example di-n-tridecyl phthalate or di Iso-tridecyl phthalate.

Examples of particularly useful synthetic carrier oils include about 5 to 35, for example 5 to 30 C ₃ -C ₆ -alkylene oxide units such as propylene oxide, n-butylene oxide and isobutylene oxide units or Alcohol-initiated polyethers containing mixtures thereof. Non-limiting examples of alcoholic starters are phenols substituted with long chain alkanols or long chain alkyl groups, where the alkyl group is preferably straight or branched C ₆ -C ₁₈ -alkyl. Preferred examples of alcoholic starters are tridecanol and nonylphenol.

Further suitable synthetic carrier oils are those described in alkoxylated alkylphenols such as DE-A 10 102 913.

Preferably, synthetic carrier oils are used. Preferred synthetic carrier oils are alkanol alkoxylates, in particular alkanol propoxylates and alkanol butoxylates.

In one particularly preferred embodiment, the carrier oil component (B) comprises C ₁ -C ₃₀ -alkanols, in particular C ₆ -C ₁₈ -alkanols, or C ₂ -C ₆₀ -alkanediols, especially C ₈ -C _24- One or more polyethers obtained from alkanediol and from 1 to 30 moles in total, in particular 5 to 30 moles of propylene oxide and / or butylene oxide. Other synthetic carrier oils and / or mineral carrier oils may be present in minor amounts in component (B).

Dispersant  Booster (Component C)

The polyisobutenes suitable for preparing the low molecular weight polyisobutyl-substituted amine dispersant boosters used as component (C) in the present invention are at least about 20 mol%, preferably at least 50 mol%, more preferably 70 Polyisobutenes comprising at least mol%, most preferably at least 80 mol%, more reactive methylvinylidene isomers (ie, having terminal vinylidene double bonds). Suitable polyisobutenes include those made using BF ₃ catalysts. The preparation of such polyisobutenes in which methylvinylidene isomers are included in high percentages in the total composition is described, for example, in US Pat. No. 4,152,499 and US Pat. Starting from an industrial C ₄ stream containing ten, such as raffinate I.

Furthermore, such polyisobutenes suitable for preparing low molecular weight polyisobutyl-substituted amine dispersant boosters used as component (C) in the present invention are oligomers of isobutene, for example triisobutene, tetraisobutene , Pentaisobutene, hexisobutene, heptisobutene, octaisobutene, nonaisobutene, decaisobutene, undecaisobutene, dodecaisobutene or mixtures thereof.

In most cases, the polyisobutene precursor is not a pure single product, but rather a mixture of compounds having a number average molecular weight of 200 to 650 Daltons. In general, the molecular weight distribution range will be a relatively narrow range with a maximum close to the stated molecular weight.

The amine component of each of the low molecular weight polyisobutyl monoamine or polyisobutyl polyamine can be derived from ammonia, monoamine or polyamine.

Monoamine or polyamine components include amines having 1 to about 12 amine nitrogen atoms and 1 to 40 carbon atoms. The carbon: nitrogen ratio may be about 1: 1 to about 10: 1. In general, monoamines will contain 1 to about 40 carbon atoms and polyamines will contain 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms.

The amine component can be a pure single product or a mixture of compounds having a large amount of the selected amine.

If the amine component is a polyamine, it may preferably be a polyalkylene polyamine including an alkylene diamine. Preferably, the alkylene group will contain 2 to 6 carbon atoms, more preferably 2, 3 or 4 carbon atoms. Examples of such polyamines include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine. Preferred polyamines are ethylene diamine and diethylene triamine.

Particularly preferred polyisobutyl polyamines include polyisobutyl ethylene diamine and polyisobutyl diethylene triamine. Polyisobutyl groups are substantially saturated.

The polyisobutyl monoamines or polyisobutyl polyamines used as component (C) in the fuel additive compositions of the present invention correspond by conventional procedures known in the art, in particular similarly to the teachings of EP-A 0 244 616. Is prepared by hydroformylation of the highly reactive polyisobutenes and subsequent reductive amination. In more detail, highly reactive polyisobutenes having a high content of terminal vinylidene double bonds, especially terminal vinylidene double bonds of at least 70 mol%, more preferably at least 80 mol%, are hydroformylation catalysts, for example In the presence of a suitable rhodium or cobalt catalyst, it is preferably reacted with carbon monoxide and hydrogen in an inert solvent such as a hydrocarbon solvent, typically at a temperature in the range from 80 to 200 ° C. and a CO / H ₂ -pressure of up to 600 bar. The resulting oxo intermediate is then in the presence of hydrogen, a suitable nitrogen compound, a suitable catalyst, such as lyny nickel or lyny cobalt, preferably in an inert solvent such as a hydrocarbon solvent or an alcohol solvent, typically in the range from 80 to 200 ° C. Undergo a reductive amination reaction at a temperature of and a H ₂ -pressure of 80 to 300 bar.

The amine portion of the molecule may have one or more substituents. Thus, the carbon and / or especially nitrogen atoms of the amines are hydrocarbyl groups having 1 to about 10 carbon atoms, acyl groups having 2 to about 10 carbon atoms, and monoketo, monohydroxy, mononitro, mono Cyano, lower alkyl and lower alkoxy derivatives thereof. As used herein, "lower" means a group containing from 1 to about 6 carbon atoms. One or more hydrogen atoms on one of the basic nitrogen atoms of the polyamine may not be substituted such that one or more of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen atom.

The polyamines used within the scope of the invention as amine components for polyisobutyl polyamines may be polyalkylene polyamines, which include substituted polyamines such as alkyl and hydroxyalkyl-substituted polyalkylene polyamines. do. Among the polyalkylene polyamines, mention may be made of polyalkylene polyamines, in particular C ₂ -C ₃ alkylene polyamines, containing 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms. Preferably, the alkylene group contains 2 to 6 carbon atoms and preferably there are 2 to 3 carbon atoms between the nitrogen atoms. Such groups include ethylene, 1,2-propylene, 2,2-dimethylpropylene, trimethylene, 1,3- (2-hydroxy) -propylene.

Examples of such polyamines are ethylene diamine, diethylene triamine, di (trimethylene) triamine, 1,2-propylene diamine, 1,3-propylene diamine, dipropylene triamine, triethylene tetraamine, tripropylene tetraamine, Tetraethylene pentamine, pentaethylene hexamine, hexamethylene diamine, and 3- (N, N-dimethylamino) propyl-amine. Such amines encompass isomers such as branched polyamines and the aforementioned substituted polyamines, including hydroxy- and hydrocarbyl-substituted polyamines.

The amine component for polyisobutyl monoamine or polyisobutyl polyamine can also be derived from heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocycle is one containing oxygen and / or nitrogen It includes five or six member rings above. Such heterocyclic rings may be saturated or unsaturated and substituted with the groups defined above.

Examples of heterocyclic compounds include 2-methylpiperazine, N- (2-hydroxyethyl) -piperazine, 1,2-bis- (N-piperazinyl) ethane, N, N'-bis (N- Piperazinyl) -piperazine, 2-methylimidazoline, 3-aminopiperidine, 3-aminopyridine, N- (3-amino-propyl) -morpholine, N- (beta-aminoethyl) piperazine , N- (betaaminoethyl) piperidine, 3-amino-N-ethylpiperidine, N- (betaaminoethyl) morpholine, N, N'-di (beta-aminoethyl) -piperazine, N , N'-di (beta-aminoethyl) imidazolidone-2, 1,3-dimethyl-5 (beta-amino-ethyl) hexahydrotriazine, N- (betaaminoethyl) -hexahydrotriazine, 5- (beta-aminoethyl) -1,3,5-dioxazine may be mentioned.

Alternatively, the amine component for the polyisobutyl monoamine can be derived from a monoamine having the formula HNR ¹ R ² , wherein R ¹ and R ² are independently hydrogen and hydrocarbyl of 1 to about 20 carbon atoms. And R ¹ and R ² can be taken together to form one or more five or six membered rings containing up to about 20 carbon atoms. Preferably, R ¹ is hydrogen and R ² is a hydrocarbyl group having 1 to about 10 carbon atoms. More preferably, R ¹ and R ² are hydrogen. Hydrocarbyl groups can be straight or branched and can be aliphatic, cycloaliphatic, aromatic or combinations thereof. Hydrocarbyl groups may also contain one or more oxygen atoms.

Typical primary amines are N-methylamine, N-ethylamine, Nn-propylamine, N-isopropylamine, Nn-butylamine, N-isobutylamine, N-sec-butylamine, N-tert-butylamine , Nn-pentylamine, N-cyclopentylamine, Nn-hexylamine, N-cyclohexylamine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N-benzylamine, N- (2-phenylethyl) amine, 2-aminoethanol, 3-amino-1-propanol, 2- (2-amino-ethoxy) ethanol, N- (2-methoxyethyl) amine, N- (2 -Ethoxyethyl) amine, and the like. Preferred primary amines are N-methylamine, N-ethylamine and N-n-propylamine.

Typical secondary amines are N, N-dimethylamine, N, N-diethylamine, N, N-di-n-propylamine, N, N-diisopropylamine, N, N-di-n-butylamine , N, N-di-sec-butylamine, N, N-di-n-pentylamine, N, N-di-n-hexylamine, N, N-dicyclohexylamine, N, N-dioctylamine , N-ethyl-N-methylamine, N-methyl-Nn-propylamine, Nn-butyl-N-methylamine, N-methyl-N-octylamine, N-ethyl-N-isopropylamine, N-ethyl -N-octylamine, N, N-di- (2-hydroxy-ethyl) amine, N, N-di (3-hydroxypropyl) amine, N, N-di (ethoxyethyl) amine, N, N-di- (propoxyethyl) amine, and the like. Preferred secondary amines are N, N-dimethylamine, N, N-diethylamine and N, N-di-n-propylamine.

Cyclic secondary amines can also be used to form the polyisobutyl monoamines or polyisobutyl polyamines used in the present invention. In such cyclic compounds, R ¹ and R ² of the above formula together form one or more five or six membered rings containing up to about 20 carbon atoms. Rings containing amine nitrogen atoms are generally saturated but may be fused to one or more saturated or unsaturated rings. The ring may be substituted with a hydrocarbyl group of 1 to about 10 carbon atoms and may contain one or more oxygen atoms.

Suitable cyclic secondary amines include piperidine, 4-methylpiperidine, pyrrolidine, morpholine, 2,6-dimethylmorpholine, and the like.

The number average molecular weight M _N of the polyisobutyl group in the polyisobutyl monoamine, polyisobutyl polyamine and polyisobutyl-substituted Mannich adduct used as the dispersant booster component (C) in the present invention is 200 to 650 Daltons, Preferably it is 250 to 600 Daltons, most preferably 300 to 5500 Daltons. As already mentioned for polyisobutene precursors, polyisobutyl monoamines, polyisobutyl polyamines and polyisobutyl-substituted Mannich adducts are mostly not pure single products but rather have a number average molecular weight as indicated above. Mixture of compounds. In general, the molecular weight distribution range will be a relatively narrow range with a maximum close to the stated molecular weight.

In one particularly preferred embodiment, the dispersant booster component (C) is polyisobutyl having the number average molecular weight M _N of the polyisobutyl groups of 200 to 650 Daltons, preferably 250 to 600 Daltons, most preferably 300 to 550 Daltons. Monoamine. Said polyisobutyl monoamine is preferably prepared on the basis of ammonia and / or preferably by hydroformylation and subsequent reductive amination of the corresponding highly reactive polyisobutene as described in EP-A 0 244 616. . More specifically, highly reactive polyisobutenes having a high content of terminal vinylidene double bonds, especially terminal vinylidene double bonds of at least 70 mol%, more preferably at least 80 mol%, are hydroformylation catalysts, for example In the presence of a suitable rhodium or cobalt catalyst, it is preferably reacted with carbon monoxide and hydrogen in an inert solvent such as a hydrocarbon solvent, typically at a temperature in the range from 80 to 200 ° C. and a CO / H ₂ -pressure of up to 600 bar. The resulting oxo intermediate is then in the presence of hydrogen, a suitable nitrogen compound, a suitable catalyst, such as lyny nickel or lyny cobalt, preferably in an inert solvent such as a hydrocarbon solvent or an alcohol solvent, typically in the range from 80 to 200 ° C. Undergo a reductive amination reaction at a temperature of and a H ₂ -pressure of 80 to 300 bar.

Mannich adducts suitable as component (C) of the invention are (i) polyisobutyl in the aromatic ring system, preferably having a number average molecular weight M _N of from 200 to 650 Daltons derived from the highly reactive polyisobutene as defined above In addition to substituents, one or more, for example one, two or three C ₁ to C ₇ alkyl substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl 1 to 2 moles of one or more polyisobutyl phenols, which may have n-pentyl or n-hexyl, (ii) 1 to 3 moles of one or more C ₁ to C ₆ aldehydes such as formaldehyde, acetaldehyde, and Propionaldehyde (which may be used in the form of oligomers or polymers, such as paraformaldehyde) and (iii) one to three moles of one or more primary or secondary amines of the formula HNR ³ R ⁴ , wherein R ³ is hydrogen, C ₁ to C ₂₀ alkyl residue or C ₃ within the C ₂₀ cycloalkyl represents an alkyl moiety, R ⁴ is C ₁ to C ₂₀ alkyl residue or a C ₃ to represent a C ₂₀ cycloalkyl residue, two residues R ³ and R ⁴ to form a ring system together with the nitrogen atom to which they are attached And / or independently of one another may be interrupted by one or more oxygen atoms and / or an imino group of the formula -NR ^5- (R ⁵ represents hydrogen or a C ₁ to C ₄ alkyl group), and / or R ⁴ May be terminated by a —NH ₂ group of ₂ ). Such Mannich adducts are known in the art, for example in WO 04/050806.

Examples of straight and branched chain primary amines of the formula HNR ³ R ⁴ include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine , n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, 3-propylheptylamine, n-decylamine, n-undecylamine, n Dodecylamine, n-tridecylamine, iso-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nona Decylamine and n-eicosylamine.

Examples of linear, branched and cyclic secondary amines of the formula HNR ³ R ⁴ are dimethylamine, diethylamine, di n-propylamine, di-iso-propylamine, di-n-butylamine, di-iso- Butylamine, di-sec-butylamine, di-tert-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di- (2- Ethylhexyl) amine, di-n-nonylamine, di- (3-propylheptyl) amine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, di-n-tri Decylamine, di-iso-tridecylamine, di-n-tetradecylamine, di-n-pentadecylamine, di-n-hexadecylamine, di-n-heptadecylamine, di-n-octadecylamine , Di-n-nonadecylamine, di-n-eicosylamine, cyclooctylamine and cyclodecylamine.

Examples of amines of formula HNR ³ R ⁴ which may be interrupted by an imino group of formula -NR ⁵ -and / or terminated with a second -NH ₂ group are N- (3,3-dimethylamino) propylamine, 1,2 Ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

Typical examples of Mannich adducts suitable as component (C) include (i) one mole of 4-polyisobutylphenol (M _N = 420 of the polyisobutyl group) and (ii) one mole of paraformaldehyde and ( iii) the reaction product of 1 mole of dimethylamine or di-n-butylamine or di (2-ethylhexyl) amine. Further typical examples of Mannich adducts suitable as component (C) include (i) 2 moles of 4-polyisobutylphenol (M _N = 420 of polyisobutyl groups) and (ii) 2 moles of paraformaldehyde. And (iii) 1 mole of methylamine or n-butylamine or 2-ethylhexylamine or 3- (N, N-dimethylamino) propylamine.

In the fuel additive composition of the present invention, the dispersant component (A) is composed of polyisobutyl monoamine, polyisobutyl polyamine, polyisobutylphenol, aldehyde and monoamine in combination with low molecular weight polyisobutyl monoamine (C). Mannich adducts, or Mannich adducts of polyisobutylphenol, aldehydes and polyamines, or mixtures of the aforementioned dispersant types.

In addition, in the fuel additive composition of the present invention, the dispersant component (A) is combined with a low molecular weight polyisobutyl polyamine (C), polyisobutyl monoamine, polyisobutyl polyamine, polyisobutylphenol, aldehyde and monoamine Mannich adducts of, or Mannich adducts of polyisobutylphenol, aldehydes and polyamines, or mixtures of the aforementioned dispersant types.

In addition, in the fuel additive composition of the present invention, the dispersant component (A) is combined with a Mannich adduct (C) of low molecular weight polyisobutylphenol, aldehyde and monoamine, polyisobutyl polyamine, polyisobutyl polyamine , Mannich adducts of polyisobutylphenol, aldehydes and monoamines, or mannich adducts of polyisobutylphenol, aldehydes and polyamines, or mixtures of the aforementioned dispersant types.

In addition, in the fuel additive composition of the present invention, the dispersant component (A) is polyisobutyl monoamine, polyisobutyl polyamine, which is combined with Mannich adducts (C) of low molecular weight polyisobutylphenol, aldehyde and polyamine, Mannich adducts of polyisobutylphenol, aldehydes and monoamines, or Mannich adducts of polyisobutylphenol, aldehydes and polyamines, or mixtures of the aforementioned dispersant types.

In one preferred embodiment, the dispersant component (A) and the dispersant booster component (C) comprise solely polyisobutyl monoamine or polyisobutyl polyamine species having the same monoamine or polyamine end groups. The end group is preferably an NH ₂ group derived from ammonia.

For the same amine end groups for polyisobutyl amines, the dispersant component (A) and the dispersant booster component (C) typically form a mixture of homologue polyisobutyl amines that exhibit a bimodal molecular weight distribution. This is the case for mixtures of Mannich adducts having the same methyleneamino end groups for both components (A) and (C) based on homologue polyisobutylphenol. Bimodal molecular weight distribution is generally characterized by asymmetric graphs (peaks) of fractions against molecular weight plots from assays such as gel permeation chromatography ("GPC"), which are used for the determination of instant M _N values in the case of organic polymers. . Small differences in molecular weight create shoulders of the peaks; The larger the difference, the shoulder forms the second peak. The situation can be described in mathematical terms as follows: The first deviation of the graph represents two maximums, while the first deviation of the monomodal graph represents only one maximum and one minimum. In the case of bimodal molecular weight distribution, components (A) and (C) are prepared by the same polymerization of isobutene and subsequent amination reactions or by the same preparation of polyisobutylphenol from isobutene, for example by chromatography or fractional distillation. It can be prepared with or without separation of the two species having a different number average molecular weight; The separation may take place before or after the amination step or the Mannich addition reaction. Alternatively, components (A) and (C) can be prepared separately from component (B) and subsequently mixed with component (B).

Fuel additive composition

The fuel additive composition of the present invention may be formulated as a concentrate using an inert, stable lipophilic (ie, soluble in fuel) organic solvent boiling in the range of about 65 to 205 ° C. Preferably, aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene or high boiling aromatic or aromatic thinners are used. In addition, aliphatic alcohols having about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol, 2-ethylhexanol, and the like, are suitable for use in such concentrates with hydrocarbon solvents. In concentrates, the amount of fuel additive composition of the present invention may typically be at least 10% to about 90% by weight, for example 40 to 85% or 50 to 80% by weight.

In gasoline fuels, other fuel additives, such as oxygenates, such as tert-butyl methyl ether, antiknock agents, such as methylcyclopentadienyl manganese tricarbonyl, and other dispersants, together with the additives of the present invention Detergents such as various hydrocarbyl amines, succinimides or polyetheramines, ie hydrocarbyl poly (oxyalkylene) amines, can be used. A list of suitable other dispersant / detergent additives is provided, for example, in WO 00/47698 or EP-A 1 155 102.

Lead scavengers such as aryl halides such as dichlorobenzene, or alkyl halides such as ethylene dibromide may also be included. There may also be antioxidants, metal deactivators, pour point inhibitors, corrosion inhibitors and demulsifiers.

In a particularly preferred embodiment, the weight ratio of the dispersant component (A) to the dispersant booster component (C) is in the range of 0.1: 1 to 10: 1, in particular 0.3: 1 to 7: 1 so that the best of the intake valve cleaning performance of gasoline fuel Provide improvement.

Interaction between the three components (A), (B) and (C) with each other is necessary to achieve the desired improvement in suction valve cleaning performance. In the fuel additive composition of the present invention, the dispersant booster component (C) may exhibit a synergistic effect in this respect when used with the components (A) and (B) of the fuel additive composition of the present invention.

Fuel composition

Fuel additive compositions of the present invention can be used in liquid hydrocarbon distillate fuels, which generally boil in the gasoline range. It is basically suitable for use in all kinds of gasoline, including "light" and "heavy" gasoline species. Gasoline fuels may also contain other fuel components such as ethanol.

The appropriate concentration of the fuel additive composition of the present invention necessary to achieve the desired intake valve cleaning performance depends on the type of fuel used and may also be influenced by the presence of other detergents, dispersants and other additives and the like. However, in general, 80 to 8000 ppm by weight, in particular 180 to 2600 ppm by weight, of fuel additive compositions of the present invention per part of base fuel are necessary to achieve the best results.

In a particularly preferred embodiment, the dispersant component (A) is present at a level of more than 20 to 3000 ppm, in particular 70 to 800 ppm, in the fuel composition of the invention and the carrier oil component (B) is 50 to 2000 ppm, in particular 100 to It is present at the level of 600 ppm and the amine component (C) is present at the level of 10 to 3000 ppm, in particular 30 to 1200 ppm (all ppm values are by weight).

Typically, gasoline fuels that can be used according to the present invention additionally exhibit one or more of the following features:

The aromatic content of the gasoline is preferably 50 kV volume% or less, more preferably 45 kV volume% or less. The preferred range of aromatic content is 1 to 45 kV volume%, especially 5 to 40 kV volume%.

The sulfur content of the gasoline is preferably 100 ppm by weight or less, more preferably 50 ppm by weight or less. The preferred range of sulfur content is from 0.5 to 150 ppm by weight, in particular from 1 to 100 ppm by weight.

Gasoline has an olefin content of 21 vol% or less, preferably 18 vol% or less, more preferably 10 vol% or less. The preferred range of olefin content is from 0.1 to 21 kPa volume, in particular from 2 to 18 kPa volume.

Gasoline has a benzene content of 1.0 kPa volume or less, preferably 0.9 kPa volume or less. The preferred range of benzene content is from 0 to 1.0 volume percent, preferably from 0.05 to 0.9 volume percent.

Gasoline has an oxygen content of at most 45% by weight, preferably 0 to 45% by weight, most preferably 0.1 to 2.7% by weight (first type) or most preferably 2.7 to 45% by weight (second type). . The second type of gasoline mentioned above is a mixture of lower alcohols such as methanol or in particular ethanol (preferably derived from natural sources such as plants) and mineral oil based gasoline, ie ordinary gasoline made from crude oil. An example of such gasoline is a mixture of "E 85", 85% by volume ethanol and 15% by volume mineral oil based gasoline.

The content of alcohols, in particular lower alcohols, and ethers in the first type of gasoline mentioned in the paragraph above is generally relatively low. Typical maximum content is 3% by volume for methanol, 5% volume% for ethanol, 10% volume% for isopropanol, 7% volume% for tert-butanol, 10% volume% for isobutanol and 5 in the molecule 15% by volume for ethers containing more than one carbon atom.

For example, the aromatic content is 38 kPa or less, at the same time the olefin content is 21 vol% or less, the sulfur content is 50 kPappm or less, the benzene content is 1.0 kPa or less, and the oxygen content is 0.1 to 2.7 wt%. Gasoline can be applied.

The summer vapor pressure of gasoline is generally 70 kPa or less (at 37 ° C), preferably 60 kPa or less.

The research octane number (“RON”) of gasoline is generally 90 to 100. Typical ranges of the corresponding motor octane number (“MON”) are 80 to 90.

This property is determined by conventional methods (DIN EN 228).

Internal combustion engine

The dispersant booster component (C) is preferably used as an intake valve cleaning booster according to the invention in a gasoline-operated port fuel injection internal combustion engine which is different from the direct injection spark ignition engine in terms of construction and mode of operation.

Experiment part

The following examples are presented to illustrate specific embodiments of the invention and should not be construed as limiting the scope of the invention in any way.

Example  1 and 2: intake valve Of deposits ("IVD")  Measure

In a Mercedes-Benz M 102E type gasoline-operated internal combustion engine according to test procedure CEC F-05-A-93 (Examples 1a and 1b) and in accordance with test procedure CEC F-20-A-98 The intake valve deposits were measured in gasoline-operated internal combustion engines (Examples 2a and 2b). General Eurosuper gasoline according to EN 228 was used as the base fuel. Deposits on the four valves of the engine were measured and their average value calculated.

The following additives were used:

A1: polyisobutyl monoamine based on highly reactive polyisobutene with 80% by weight of methylvinylidene content, M _N = 1000 and hydroformylation followed by reductive amination with ammonia

B1: polyether carrier oil obtained from tridecanol and 22 moles of butylene oxide

C1: polyisobutyl monoamine based on highly reactive polyisobutene with a content of 80 mol% methylvinylidene, M _N = 420 and hydroformylation followed by reductive amination with ammonia

Example 1a (comparative)

The Mercedes Benz M 102E engine was operated using Eurosuper Gasoline Fuel containing 300 ppm A1 and 75 ppm B1 for 60 hours in accordance with CEC F-05-A-93. As a result, the following IVD values were obtained: 12 mg, 20 mg, 67 mg, 8 mg; Average: 21 mg. The same test without any additives resulted in an average IVD value of 153 mg.

Example 1b (according to the invention):

The same Mercedes Benz M 102E engine was operated using Eurosuper gasoline fuel containing 300 ppm A1, 75 ppm B1 and 50 mg C1 for 60 hours according to CEC F-05-A-93. As a result, the following IVD values were obtained: 3 mg, 0 mg, 12 mg, 10 mg; Average: 6 mg.

Example 2a (comparative)

The Mercedes Benz M 111 engine was operated using Eurosuper Gasoline Fuel containing 400 ppm A1 and 100 ppm B1 for 60 hours according to CEC F-20-A-98. As a result, the following IVD values were obtained (measured twice): 143/175 mg, 73/164 mg, 55/68 mg, 156/148 mg; Average: 123 mg. The same test without any additives resulted in an average IVD value of 359 mg.

Example 2b (according to the invention):

The same Mercedes Benz M 111 engine was operated using Eurosuper Gasoline Fuel containing 300 ppm A1, 75 ppm B1 and 50 mg C1 for 60 hours according to CEC F-20-A-98. As a result, the following IVD values were obtained: 80/87 mg, 46/42 mg, 73/48 mg, 125/135 mg; Average: 80 mg.

Claims (11)

As a fuel additive composition,
(A) Mannich adduct of polyisobutyl monoamine, polyisobutyl polyamine, polyisobutylphenol, aldehyde and monoamine, wherein the number average molecular weight M _N of the polyisobutyl group is 650-1800 Daltons, respectively, And one or more nitrogen-containing dispersants selected from Mannich adducts of polyisobutylphenol, aldehydes and polyamines,
(B) at least one carrier oil, substantially free of nitrogen, selected from synthetic and mineral carrier oils, and
(C) polyisobutyl monoamine, polyisobutyl polyamine, mannich adduct of polyisobutylphenol, aldehyde and monoamine, and polyiso, wherein the number average molecular weight M _N of the polyisobutyl group is 200 to 650 Daltons, respectively. One or more dispersant boosters selected from Mannich adducts of butylphenol, aldehydes and polyamines
Lt; / RTI >
Provided that the difference between the M _N of the polyisobutyl group of component (A) and the M _N of the polyisobutyl group of component (C) is greater than 100 Daltons. The fuel additive composition of claim 1, wherein the dispersant booster component (C) comprises at least one polyisobutyl monoamine having a number average molecular weight M _N of polyisobutyl groups of 250 to 600 Daltons. The fuel additive composition of claim 1 or 2, wherein the dispersant component (A) comprises at least one polyisobutyl monoamine having a number average molecular weight M _N of polyisobutyl groups of 700 to 1500 Daltons. 4. The dispersant component (A) and the dispersant booster component (C) alone comprise polyisobutyl monoamine or polyisobutyl polyamine species having the same monoamine or polyamine end groups. The fuel additive composition. The dispersant component (A) and / or dispersant booster component (C) is prepared by hydroformylation and subsequent reductive amination of the corresponding highly reactive polyisobutene. Fuel additive composition. The fuel additive composition according to any one of claims 1 to 5, wherein the weight ratio of the dispersant component (A) to the dispersant booster component (C) is in the range of 0.1: 1 to 10: 1. The carrier oil component (B) according to any one of claims 1 to 6, wherein the carrier oil component (B) is from C ₁ -C ₃₀ -alkanol or C ₂ -C ₆₀ -alkanediol and in total 1 to 30 moles of ethylene oxide and And / or at least one polyether obtained from propylene oxide and / or butylene oxide. A fuel composition comprising a large amount of liquid fuel in the gasoline boiling range and a small amount of the fuel additive composition according to any one of claims 1 to 7. 9. The dispersant component (A) is present at a level of 20 to 3000 ppm, the carrier oil component (B) is present at a level of 50 to 2000 ppm and the dispersant booster component (C) is 10 to 3000 ppm. The fuel composition is present at the level of. (A) Mannich adducts of polyisobutyl monoamine, polyisobutyl polyamine, polyisobutylphenol, aldehyde and monoamine, and polyiso, wherein the number average molecular weight M _N of the polyisobutyl group is 650-1800 Daltons, respectively Gasoline boiling ranges containing small amounts of one or more nitrogen-containing dispersants selected from mannich adducts of butylphenol, aldehydes and polyamines, and (B) one or more carrier oils substantially free of nitrogen, selected from synthetic carrier oils and mineral carrier oils. Polyisobutyl monoamine, polyisobutyl polyamine, wherein the number average molecular weight M _N of (C) polyisobutyl groups, as described in claim 1, as a dispersant booster in an internal combustion engine operated on liquid fuel, is 200-650 Daltons each, Mannich adducts of polyisobutylphenol, aldehydes and monoamines, or bays of polyisobutylphenol, aldehydes and polyamines Hi adduct purpose. (C) Low molecular weight polyisobutyl monoamine, polyisobutyl polyamine, polyisobutylphenol, aldehyde and monoamine according to claim 10 as intake valve cleaning boosters in a gasoline operated port fuel injection internal combustion engine. Use of adducts or Mannich adducts of polyisobutylphenols, aldehydes and polyamines.