EP0704519B1 - Mixture of amines, hydrocarbonpolymers and carrier oils, suitable as fuel and lubricant additive - Google Patents

Description

(A) mindestens einem Amin, welches einen Kohlenwasserstoffrest mit einem mittleren Molekulargewicht von 500 bis 10000 trägt,

(B) mindestens einem Kohlenwasserstoffpolymer mit einem mittleren Molekulargewicht von 300 bis 10000, welches in nicht hydrierter oder in hydrierter Form vorliegen kann, und

(C) Trägerölen

mit einem Gew.-Verhältnis der Komponente A zur Komponente B von 80:20 bis 60:40, insbesondere 77:23 bis 65:35.The present invention relates to a new mixture of essentially suitable as a fuel and lubricant additive

(A) at least one amine which carries a hydrocarbon radical with an average molecular weight of 500 to 10,000,

(B) at least one hydrocarbon polymer with an average molecular weight of 300 to 10,000, which can be in non-hydrogenated or in hydrogenated form, and

(C) carrier oils

with a weight ratio of component A to component B of 80:20 to 60:40, in particular 77:23 to 65:35.

The invention further relates to the use of the mixture as Fuel and lubricant additives and fuels for gasoline engines and lubricant compositions which the blend in effective Amounts included.

Carburetor and intake system of gasoline engines, but also injection systems for fuel metering in petrol and diesel engines are increasingly contaminated by impurities that through dust particles from the air, unburned hydrocarbon residues out of the combustion chamber and into the carburetor Vent gases are caused from the crankcase.

The residues adsorb fuel and shift the air-fuel ratio at idle and in the lower part-load range, so that the mixture fatter, the combustion incomplete and again the proportions of unburned or partially burned hydrocarbons increase in exhaust gas and gasoline consumption increases.

It is known that by adding detergents, the inlet system gasoline engines can be kept clean (see e.g. M. Rosenbeck in catalysts, surfactants, mineral oil additives, editors J. Falbe, U. Hasserodt, pp. 223 f., Thieme Verlag, Stuttgart 1978, and Ullmann's Encyclopedea of Industrial Chemistry, Vol. A 16, 719 ff, 1990, VCH publishing company). Emissions and This reduces fuel consumption and driving behavior improved. The molecular construction principle of such detergents can be generally described as linking polar structures with mostly higher molecular lipophilic residues. Representative for this are e.g. Products based on polyisobutene with amine groups as polar groups, as in EP-A 244 616 (1) described.

The document (1) further teaches that in fuel additives about 50% by weight of the active substance, i.e. the polyisobutylamine, can be replaced by polyisobutene without loss of effectiveness can; such a replacement is primarily for cost reasons. To improve the effectiveness of certain amounts of polyisobutene no indication is given.

Another important additive component for fuels are so-called carrier oils. These carrier oils are usually high-boiling, thermostable liquids. EP-B 356 726 (2) discloses esters of aromatic polycarboxylic acids with long-chain alcohols as carrier oils. EP-A 374 461 (3) describes combinations of polyethers based on propylene oxide and / or butylene oxide with a molecular weight of at least 500 with esters of mono- or polycarboxylic acids and alkanols of the polyols, these esters having a minimum viscosity of 2 mm ² / s at 100 ° C, described, which increase the efficiency of the detergent via synergistic mechanisms of action. US Pat. No. 5,006,130 (4) discloses mixtures of aliphatic alkylene polyamines with at least one oil-soluble synthetic or mineral carrier oil.

WO-A 91/03529 (5) teaches the combination of detergents which carry certain amino groups, with polyether alcohols as carrier oils. This combination is particularly less than its individual components to increase the octane requirement (ORI, Octane Requirement Increase) caused by deposits of fuel or the additives originate from engine parts. A new engine only reaches its final octane requirement after a considerable period of time, which can then be considerably higher than at the beginning. In general, additives should at least not increase this effect.

The known additives of the prior art do not yet show the optimal cleaning effect in the engine, especially the prevention or reduction of valve deposits is still in need of improvement.

The object of the present invention was therefore to force and Lubricant additives with improved effectiveness as detergents to provide.

Accordingly, the mixture defined at the outset was found, which characterized in that a component oil mixture as component C. from (b) polyethers based on propylene oxide and / or butylene oxide and (d) esters of mono- or polycarboxylic acids and alkanols or polyols is used.

Component A

Component A is primarily used as a detergent in fuels effective. As component A such amines come into question, which one Hydrocarbon residue with an average molecular weight of 500 to 10,000, preferably from 600 to 2500 and particularly preferred from 700 to 1500.

The hydrocarbon residue is usually branched. In general, such a residue is obtainable by polymerizing olefins. These olefins are preferably C ₂ -C ₆ -olefins, such as ethylene, propylene, 1-butene, 1-pentene, but particularly preferably isobutene. Both homopolymers and copolymers are possible, for example polymers of 70 to 100% by weight of isobutene and 0 to 30% by weight of 1-butene. Due to their manufacturing process, these polyolefins generally consist of a mixture of compounds of different molecular weights.

In a manner known per se, these polyolefins after chlorination be implemented with amines. However, hydroformylation is preferred of the polyolefin and amination of the resultant Aldehyde and alcohol mixture under hydrogenating conditions, such as described for example in (1), since this route to chlorine-free Products. The amine group of detergent A conducts of known amines such as ammonia, primary amines such as methylamine, ethylamine, butylamine, hexylamine, octylamine, secondary amines such as dimethylamine, diethylamine, dibutylamine, Dioctylamine or heterocycles such as piperazine, pyrrolidine, Morpholine, optionally further inert substituents can wear from. Ammonia is particularly preferred.

A very particularly preferred embodiment for the component A is a medium molecular weight polyisobutylamine from 700 to 1500, with up to 20% by weight of the isobutene units can be replaced by 1-butene units.

Component B

As hydrocarbon polymer B are particularly suitable olefin polymers described as a precursor to component A. Such olefin polymers have a medium as component B. Molecular weight of preferably 400 to 1750, in particular from 500 to 1500. The hydrocarbon polymer B can still contain olefinic double bonds due to production; such However, double bonds can also have been hydrogenated. The Component B can either be added separately or by suitable reaction control in the production of component A from an excess of the olefin polymers described in the mixture according to the invention can be introduced.

A very particularly preferred embodiment for the component B is a medium molecular weight polyisobutene from 500 to 1500, with up to 20% by weight of the isobutene units can be replaced by 1-butene units.

Both component A and component B can each Mixtures of different individual compounds.

Component C

(b) Polyether auf Basis von Propylenoxid und/oder Butylenoxid, insbesondere solche mit einer Molmasse von mindestens 500; insbesondere kommen hier Polyalkylenoxide in Betracht, die auf einem mittel- oder langkettigen Alkanol oder Alkandiol, einem von der Kettenlänge vergleichbaren Amin oder einem Alkylphenol, z.B. auf 1,6-Hexandiol, 1,8-Octandiol, iso-Tridecanol, iso-Nonylphenol, iso-Dedecylphenol oder iso-Tridecylamin, gestartet wurden. Pro Startermolekül können meist bis zu 50 mol, insbesondere 8 bis 30 mol, Propylenoxid oder Butylenoxid oder eine Mischung hieraus, welche blockartig oder zufällig verteilt eingebaut wird, umgesetzt werden;

(d) Ester aus Mono- oder Polycarbonsäuren mit Alkanolen oder Polyolen, insbesondere solche mit einer Mindestviskosität von 2 mm²/s bei 100°C; als Mono- oder Polycarbonsäuren können aliphatische oder vorzugsweise aromatische eingesetzt werden, als Esteralkohole bzw. -polyole eignen sich vor allem langkettige Vertreter mit beispielsweise 6 bis 24 C-Atomen; typische Vertreter der Ester (d) sind Adipate, Phthalate, iso-Phthalate, Terephthalate und Trimellitate des iso-Octanols, iso-Nonanols, iso-Decanols und des iso-Tridecanols.

Suitable carrier oils C for the mixture of (b) polyethers and (d) esters are:

(b) polyethers based on propylene oxide and / or butylene oxide, in particular those with a molecular weight of at least 500; polyalkylene oxides which are based in particular on a medium-chain or long-chain alkanol or alkanediol, an amine comparable in chain length or an alkylphenol, for example on 1,6-hexanediol, 1,8-octanediol, isotridecanol, isononylphenol, iso-dedecylphenol or iso-tridecylamine. Up to 50 mol, in particular 8 to 30 mol, of propylene oxide or butylene oxide or a mixture thereof, which is incorporated in blocks or randomly, can usually be reacted per starter molecule;

(d) esters of mono- or polycarboxylic acids with alkanols or polyols, especially those with a minimum viscosity of 2 mm ² / s at 100 ° C; aliphatic or preferably aromatic mono- or polycarboxylic acids can be used; long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols; typical representatives of the esters (d) are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol.

In a particularly preferred embodiment, the component is used C is a carrier oil mixture of polyethers (b) and esters (d) a, wherein (b) and (d) preferably in a weight ratio of 20:80 to 80:20, especially 35:65 to 65:35.

Component C is usually in the mixture according to the invention in a weight ratio to the sum of amine A and Hydrocarbon polymer B from 5:95 to 85:15, in particular 20:80 until 70:30, before.

The mixture according to the invention can contain further components D wherein the amounts of D 0 to 40 wt .-%, preferably 0 to 10% by weight, based on the total weight of components A to C, be. These components D affect the properties of the mixtures according to the invention with regard to their use in Fuels only to a small extent.

Component D comprises additives known per se for mixtures, the fuels and lubricants are added. Among them are especially corrosion inhibitors, demulsifiers, detergents or dispersants such as amides and imides of polyisobutyl succinic anhydride to understand.

The present invention also relates to the use of described mixture of components A to C as a force and Lubricant additives.

The present invention further relates to fuels for Gasoline engines, which effective amounts of the invention Mix included.

Leaded and unleaded normal and Super gasoline into consideration. The gasoline can also use other components as hydrocarbons, e.g. Alcohols such as methanol, ethanol, tert-butanol and ethers such as methyl tert-butyl ether.

The fuels according to the invention contain the mixtures of components A to C generally in amounts of each 10 to 5000 ppm, based on the total mass, preferably 50 to 1000 ppm. The fuels according to the invention can be in addition to the above Component D described also antioxidants, e.g. N, N'-di-sec-butyl-para-phenylenediamine, and stabilizers, e.g. N, N'-disalicylidene-1,2-diaminopropane.

Components A to C can be made into clear, homogeneous solutions mix. Fuels additized with this point opposite the pure fuels significantly lower valve deposits. Furthermore, the additives do not contribute to an increase in the octane requirement (ORI) at.

The present invention further relates to lubricant compositions what effective amounts of the invention Mix included. Effective amounts are usually here 0.1 to 6 wt .-%, in particular 0.5 to 5 wt .-%, based on the Weight of the lubricant composition.

Examples Determination of valve deposits through engine tests in Mercedes-Benz M 102 E according to CEC-F-05-T-92

In the engine tests, mixtures of components A, B and C and, for comparison, mixtures of components A and C were tested for their effectiveness in keeping the intake valves clean. The fuel used was unleaded Eurosuper. Example No. component Quantity [ppm ≙ mg / kg fuel] average valve deposits [mg] For comparison: 1 A: PIBA (M approx. 1000) 300 83 C: mineral oil 300 2nd A: PIBA (M approx. 1000) 300 70 C: polyether 300 3rd A: PIBA (M approx. 1000) 300 80 C: ester 300 4th A: PIBA (M approx. 1000) 300 48 B: PIB (M approx. 1000) 150 C: polyether 150 5 A: PIBA (M approx. 1000) 300 60 B: PIB (M approx. 1000) 150 C: ester 150 according to the invention: 6 A: PIBA (M approx. 1000) 300 15 B: PIB (M approx. 1000) 100 C: polyether 100 Esters 100 7 A: PIBA (M approx. 1000) 300 7 B: PIB (M approx. 700) 100 C: polyether 100 Esters 100

The clearly higher effectiveness of the invention can be seen Mixture according to Examples 6 and 7 compared to the mixtures according to Examples 1 to 5.

Claims (9)

1. A mixture suitable as a fuel additive and lubricant additive and comprising essentially

   (A) at least one amine which carries a hydrocarbon radical having an average molecular weight of from 500 to 10,000,

   (B) at least one hydrocarbon polymer which has an average molecular weight of from 300 to 10,000 and may be present in unhydrogenated or hydrogenated form and

   (C) carrier oils,

   having a weight ratio of component A to component B of from 80:20 to 60:40, wherein a carrier oil mixture comprising (b) polyethers based on propylene oxide or butylene oxide and (d) esters of mono- or polycarboxylic acids and alkanols or polyols is used as component C.
2. A mixture suitable as a fuel additive and lubricant additive, as claimed in claim 1, which has a weight ratio of component A to component B of from 77:23 to 65:35.
3. A mixture suitable as a fuel additive and lubricant additive, as claimed in claim 1 or 2, in which a polyisobutylamine having an average molecular weight of from 700 to 1500 is used as component A, it being possible for up to 20 % by weight of the isobutene units to be replaced by 1-butene units.
4. A mixture suitable as a fuel additive and lubricant additive, as claimed in any of claims 1 to 3, in which a polyisobutene having an average molecular weight of from 500 to 1500 is used as component B, it being possible for up to 20 % by weight of the isobutene units to be replaced by 1-butene units.
5. Use of a mixture as claimed in any of claims 1 to 4 as a fuel additive or lubricant additive.
6. A fuel for gasolene engines, containing an effective amount of a mixture as claimed in any of claims 1 to 4.
7. A fuel for gasolene engines, containing from 10 to 5000 ppm of a mixture as claimed in any of claims 1 to 4.
8. A lubricant composition containing an effective amount of a mixture as claimed in any of claims 1 to 4.
9. A lubricant composition containing from 0.1 to 6 % by weight of a mixture as claimed in any of claims 1 to 4.