DE4000539A1 - FUELS FOR OTTO ENGINES - Google Patents

Description

The invention relates to fuels for gasoline engines with small amounts Amides from aminoalkylene polycarboxylic acids and secondary long-chain Amines.

Carburetor and intake system of gasoline engines, but also injection systems for fuel metering in gasoline and diesel engines are increasing Dimensions contaminated by dust particles from the Air, unburned hydrocarbon residues from the combustion chamber and those in the Carburetor-directed crankcase ventilation gases are caused.

These residues shift the air-fuel ratio at idle and in the lower part-load range, so that the mixture fatter, the combustion un more complete and again the proportions of unburned or partially burned Hydrocarbons in the exhaust gas get bigger and gasoline consumption increases.

It is known that to avoid these disadvantages, fuel additives for Keeping valves and carburetor or injection systems clean (compare e.g. M. Rossenbeck in catalysts, surfactants, mineral oil additive, ed. J. Falbe, U. Hasserodt, p. 223 f., G. Thieme Verlag, Stuttgart, 1978).

Depending on the mode of action but also on the preferred site of action There are two generations of detergent additives today.

The first generation of additives was only able to form deposits in the Prevent suction system, but not existing deposits again remove, whereas the modern second generation additives do both can effect ("keep-clean" and "clean-up effect"), namely, due to changed thermal properties, especially in areas of higher Temperatures, namely at the inlet valves.

The molecular construction principle of fuel detergents can be generalized in my opinion are given as a link between polar structures and mostly higher molecular weight, non-polar or lipophilic residues.

As representatives of the second generation of additives, in addition to products based on polyisobutenes, e.g. B. Polyisobutylamine according to DE-OS 36 11 230, in particular amides, imides and imide / amides of various Carboxylic acids and polycarboxylic acids proven.  

The well-known active ingredients based on Trillon should be emphasized here derivatives and higher branched amines as described in EP-A2-00 06 527 are described.

It has now surprisingly been found that the addition to fuels for petrol engines in amounts of 100 to 500 ppm of amides, amidammonium salts or ammonium salts of aminoalkylene polycarboxylic acids with secondary Fatty amines and their mixtures of formulas I and II

in which
A is a straight-chain or branched alkylene radical having 2 to 6 carbon atoms or the rest of the formula

and
R essentially means straight-chain aliphatic radicals, in particular alkyl radicals having 10 to 30, preferably 14 to 24, carbon atoms, the amide structures also partially or completely in the form of the ammonium salt structure of the formula

may be present, particularly effective with respect to carburetor and Valve cleaning is.  

The amides or amide ammonium salts or ammonium salts z. B. the nitrilo triacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-di amine tetraacetic acid by reacting the acids with 0.5 to 1.5 mol Amine, preferably 0.8 to 1.2 moles of amine per carboxyl group.

The reaction temperatures are about 80 to 200 ° C, where to position of the amides a continuous removal of the resulting Water of reaction takes place. However, the implementation does not have to be complete Amide can be performed, rather 0 to 100 mol .-% of the used Amine in the form of the ammonium salt.

As amines of the formula

come in particular dialkylamines into which R is a straight chain alkyl radical having 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms. In particular, dioleylamine, dipal mitinamine, dicoconut fatty amine and dibehenylamine and preferably ditallow called fatty amine.

The amides or ammonium salts of amino to be used according to the invention alkylene polycarboxylic acids of formulas I and II are used in fuels Amounts of 50 to 1000 ppm, preferably 100 to 500 ppm, are added.

Leaded and unleaded normal and super gasoline. The gasoline can also use other components as hydrocarbons, e.g. B. alcohols such as methanol, ethanol, tert-butanol as well as ethers, e.g. B. contain methyl tertiary butyl ether. In addition to the fiction according to the amides of the aminoalkylene polycarboxylic acids to be used the fuels usually have other additives such as corrosion inhibitors, stabilizers, antioxidants and / or detergents.

Corrosion inhibitors are mostly ammonium salts org. Carboxylic acid through appropriate structure of the starting compounds for film formation tend. Amines for lowering the pH are also often found in Corrosion inhibitors. Mostly used as non-ferrous metal corrosion protection heterocyclic aromatics used.

In particular, amines such as para- Phenylenediamine, dicyclohexylamine, morpholine or derivatives of these amines  call. Phenolic antioxidants such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxiphenylpropionic acid and its derivatives Fuel and lubricants added.

Other carburetor, injectror and valve detergents are also available if necessary, amides and imides of polyisobutylene succinic anhydride, poly butenepolyamines as well as long chain carbonamides and imides in fuels contain.

Examples A) Preparation of the nitriloacetic acid amides

• 1) 240 g (0.48 mol) ditallow fatty amine and 35 g (0.12 mol) ethylenedi aminotetraacetic acid were melted and heated to 190 ° C. the water of reaction formed continuously distilled off. The reaction was at about 25 hours at an acid number <5 and an amine number <1.1 terminated. By creating Water jet vacuum (2 hours, 120 ° C) became the water of reaction completely removed. 265 g of a brown, waxy one were obtained Solid which for easier handling z. B. z. B. with xylene can be diluted.
• 2) 100 g (0.2 mol) ditallow fatty amine and 14.6 g (0.05 mol) ethylene diaminotetraacetic acid were heated to 180 ° C for 8 hours. To During this time, about 50% of the amine had reacted to the amide (acid number 45.8, Theory 49.7). 97.6 g of the amide / ammonium salt were obtained as a light brown, waxy solid.
• 3) In a melt of 229.5 (0.45 mol ditallow fatty amine were 80 ° C 28.65 g (0.15 mol) of nitrilotriacetic acid (Trilon A) wear. The reaction mixture was then opened for 10 hours Heated from 180 to 190 ° C. To completely remove the Water of reaction, the product was at 120 ° C for 2 hours Water jet vacuum dried. 249 g were obtained (theory 250 g) light brown, waxy solid.

B) Testing as a valve cleaner

Claims (6)

1. Fuels for gasoline engines containing small amounts of amides, amidammonium salts or ammonium salts of aminoalkylene polycarboxylic acids of the formulas I and II and mixtures thereof, wherein A is a straight-chain or branched alkylene radical having 2 to 6 carbon atoms or the rest of the formula and
in which R independently of one another essentially means straight-chain aliphatic radicals having 10 to 30 carbon atoms, where the amide groups can also be present as alkylammonium carboxylate groups with the radicals R mentioned. 2. Fuels according to claim 1, containing amides, ammonium salts and Ammonium salts of aminoalkylene polycarboxylic acids and their mixtures, characterized in that the radical R is a straight-chain alkyl radical with 14 to 24 carbon atoms. 3. Fuels according to claim 1, containing compounds of the formula in which R denotes a straight-chain alkyl radical having 10 to 30 carbon atoms and some or all of the amide groups as dialkyl ammonium carboxylate groups of the amines can be present. 4. Fuels according to claim 1, containing the compounds of the formulas I and II in amounts of 50 to 1500 ppm, based on the fuel. 5. Fuels according to Claims 1 to 4, containing compounds of the formulas I and II, in which the rest means ditallow fatty amines. 6. Fuels according to claim 1, characterized in that they have further Fuel detergents, anti-icing agents, corrosion inhibitors and / or contain antioxidants.