SK9397A3 - Reaction products of polyisobutylenes and nitrogen oxides or mixtures of nitrogen oxides and oxygen and their use as fuel and lubricant additives - Google Patents

Abstract

The invention concerns reaction products of polyisobutylenes having an average polymerisation degree P of 10 to 100 and a proportion E of 60 to 90 % of double bonds which can be reacted with maleic acid anhydride, E corresponding to 100 % of the calculated theoretical value if each polyisobutylene molecule has a reactive double bond of this type, with nitrogen oxides or mixtures of nitrogen oxides and oxygen. These reaction products are suitable as fuel additives, in particular for spark-ignition engines, and as lubricant additives.

Description

Technical field

The invention relates to reaction products of polyisobutenes of intermediate degree of polymerization p = 10 to 100 with a proportion of E = 60 to 90% of double bonds capable of reacting with maleic anhydride, the E value of 100% corresponding to a numerical theoretical value in case each the polyisobutene molecule would have such a reactive double bond with nitrogen oxides or with a mixture of nitrogen oxides and oxygen.

The invention further relates to the use of these reaction products as additives to fuels and lubricants and to the use of fuels containing these reaction products for spark ignition engines.

BACKGROUND OF THE INVENTION

Petrol carburetors and injection systems, but also injection systems for fueling petrol and diesel (diesel) impurities consisting of dust particles from unburnt fuel residues in the combustion are loaded from the air, the space coming from the crankcase vent gases introduced by the crankcase. to the carburetor.

The residues shift the air to fuel ratio at idle and in the lower load area so that the mixture becomes richer and combustion becomes imperfect, and again the proportions of unburned or only partially combusted hydrocarbons in the exhaust gas increase and gasoline consumption increases.

It is known that fuel additives are used to prevent these deficiencies, to keep the valves and carburetors or injection system clean (M. Rossenbeck,

Katalysatoren, Tenside, Mineraloladditive, J. Falbe, U. Hasserodt, p. 223, G. Thieme Verlag, Stuttgart, 1978).

Two generations of such adjuvants are recognized by the type of action, but also by the preferred site of action of such detergent-additives.

The first generation of additives could only prevent the formation of deposits in the suction system, but not remove existing deposits, which in turn can provide second generation additives (keep cleen) and (clean-up-effect) on the basis of excellent thermal stability, especially in areas of higher temperatures, namely at the filling valves.

The principle of the molecular construction of fuel detergents can be described in some generalizations by linking polar structures to most higher molecular, non-polar or lipophilic residues.

Representatives of the second generation of additives are often polyisobutene-based products in a non-polar molecular fraction. Here, polyisobutylamine-type additives have to be highlighted again.

U.S. Pat. No. 3,576,742 (1971) discloses reaction products of long-chain branched aliphatic olefins, for example polypropylenes, polyisobutylenes, or copolymers of ethylene and isobutylene and nitrogen oxides such as detergents for lubricants. These olefins are prepared by conventional polymerization processes from low olefins having 2 to 6 carbon atoms. Thus, the occurrence of other functional groups such as hydroxyl, nitrose, nitrate, nitrite or carbonyl groups is undefined in the reaction products containing nitro groups. The structure and composition of these olefins is thus undefined.

DE-C 27 02 604 (2) of 1978 describes a process for the production of polyisobutene having a medium degree of polymerization of 10 to 100, obtaining for the first time highly reactive polyisobutenes, i.e. predominantly terminal double bonds. In contrast, the polybutenes obtained by conventional polymerization processes as in (1) show only a minor proportion of terminal double bonds.

The reaction products known from (1) containing nitro groups based on conventional polyisobutene show some effect as lubricant additives, but this effect needs to be further improved. It is also desirable that the compositions be useful as fuel additives for spark ignition engines.

It is therefore an object of the present invention to provide fuel and lubricant additives with improved performance.

In this connection, a polyolefin derivative, which can be used as an additive to fuels and lubricants, and which, in particular due to its controllability and reproducibility, has a defined structure and composition, is to be provided, in particular when polyolefin is used as starting material and in a simple one-step reaction.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides a reaction product of polyisobutenes of intermediate polymerization stage P = 10 to 100 with an E = 60 to 90% double bond, capable of reacting with maleic anhydride, wherein E = 100% corresponds to a numerical theoretical value in case each polyisobutene molecule has such reactive a double bond with nitrogen oxides or with a mixture of nitrogen oxides and oxygen.

Accordingly, the present invention relates to the above-defined reaction products of highly reactive polybutenes and nitrogen oxides, or mixtures of nitrogen oxides and oxygen.

Surprisingly, it has been found that the above reaction of the described polyisobutenes provides a product with excellent properties as fuel and lubricant additives, although the product does not contain any basic nitrogen group. In contrast to the prior art two-step process for producing (amine-containing) fuel additives based on polyolefins, the process of the invention is a simple one-step preparation process. In addition, it has surprisingly been found that the polyolefin is completely reacted to provide a reaction mixture in which the main constituents can be precisely defined by their chemical structure and composition.

Among the boron trifluoride described above, in general, the preparation process of which polyisobutenes are known for process (2), the starting material, by means of conditions such as reactive, represent in the reaction of highly reactive polyisobutenes intermediates for mineral oil auxiliaries. If these polyisobutenes are reacted (initially more appropriately referred to as oligobutenes, but this term is less commonly used in the literature) with maleic anhydride, addition compounds are formed to give high-value additives which, when reacted with amines, into lubricating oils.

This addition reaction occurs practically only between maleic anhydride and the terminal (α-terminal) double bond of polyisobutene, which protrudes from chain breaking. Also, the double bonds in the β-position may still react to some extent with maleic anhydride, and there is also no reaction in the case of standing double bonds. If the proportion of reaction-capable, predominantly terminal double bonds in polyisobutene E is labeled, W was the lubricating oil additive 100%, possible double bonds were terminal, the relative potency if all theoretically E would also be

100%. However, this does not happen in practice, as in conventional polyisobutins, in practice only values of E = W = 20 to 50 are generally achieved. This means that larger amounts of such polyisobutene / maleic anhydride mixture than theoretically at E = 100 must be used for the reaction. % needed. Polyisobutene contained in a composition which has not reacted with maleic anhydride behaves inertly in mineral oil adjuvants, preferably larger quantities must even be removed.

The average polymerization stage P is 10 to 100, preferably 15 to 40. As is always the case with such polymers, polymers with a certain spectrum of degree of polymerization are obtained. With respect to the properties of the reaction products according to the invention with nitrogen oxides or nitrogen-oxygen mixtures, the dispersion is without apparent influence, so that it is only a medium polymerization stage P which can be monitored and controlled, for example by viscosity measurement, during polymerization.

Following the intermediate polymerization stage P, the highly reactive polyisobutenes described above have a carbon number of 36 to 400, preferably 54 to 160, and an average molecular weight (determined by calculation) of 500 to 5600, preferably 750 to 2250.

By polyisobutenes as starting materials for the process according to the invention are meant not only homopolymerisates of isobutene, but also copolymers thereof with at least 80% isobutene. Suitable comonomers are in particular other olefinically unsaturated hydrocarbons having 4 carbon atoms, so that, as it is of particular technical importance, it is possible to start immediately from the so-called C ₄ sections. These sections contain, in addition to 12 to 14% butanes, 40 to 55% butenes and up to 1% butadiene, although only 35 to 45% isobutenes, but largely selective polymerizability makes the other monomers included in polymers only about 2% under polarization conditions. up to 20%. Monomers that have not reacted can be used for other purposes. Other comonomers which may be used are monomers having 3 carbon atoms, such as propane and ethylene, or mixtures thereof or monomers having 4 carbon atoms.

In this way, 60 to 90%, in many cases 75 to 90%, of isobutene with an E content in the double bonds which have reacted with maleic anhydride is obtained. A theoretical calculated value of E = 100% would accordingly mean that each poly isobutene molecule would contain such a reactive double bond. E is obtained in a simple manner most directly from the acid number of the polyisobutene / maleic anhydride adduct.

Nitrogen oxides, in particular nitrogen oxides NO, NO ₂ , N ₂ O ₃ and N ₂ O ₄ , a mixture of these oxides and mixtures of these oxides with oxygen, in particular NO with oxygen and NO ₂ with oxygen, are suitable for the reaction to the products according to the invention. When oxygen is used, the oxygen in the mixture with the oxides of nitrogen is 1 to 70% by volume, in particular 5 to 50% by volume. The mixture of nitrogen oxide with oxygen may also contain inert gases such as nitrogen; this occurs, for example, using mixtures of nitrogen oxide with air.

The reaction to the products according to the invention can be carried out under pressure or under pressure, intermittently or continuously.

To achieve a quantitative reaction, the nitrogen oxides are added at a molar ratio of polyisobutene to nitrogen oxides of 1: 2 to 1: 4, preferably 1: 2.2 to 1: 3.3. Greater surplus is not harmful.

The temperature is not critical. Varies from -30 to 150 ^e C is preferably carried out at -10 to 100 C, especially at 25 to 80 "C.

The reaction is preferably carried out in an inert solvent. Thus, for example, aliphatic hydrocarbons such as isooctane or an n-alkane mixture (e.g. C10-13), chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride or chlorobenzol, ethers such as diethyl ether, tetrahydrofuran, dioxane or tert-butyl methyl ether, esters are suitable. such as ethyl acetate or benzoic acid methyl ester; amides such as dimethylformamide or N-methylpyrrolidone; and acids such as hydrochloric acid. If the reaction products are to be used as fuel additives, it is expedient to work in the same solvent in which they are added to the fuel. In general, the amounts by weight of solvents are 50 to 90%, based on the batch as a whole. However, it is also possible to work without solvents.

A small addition of water (about 0.2 to 1% by weight, based on the polyisobutene introduced) for possible hydrolysis of the resulting nitritester is not a problem.

A reaction shaft is carried out usually by first carrying out a brief heating in vacuo at the temperature of 40 to 50 ^e C and stirred into the water of both of these measures are the oxides of nitrogen.

and then the phases are separated. In order to remove residues from the reaction mixture, the product according to the invention precipitates, the use of NO ₂ or is used, in the alkanes containing nitro groups, the main component of the compound

As a rule, the reaction, in particular in the form of a mixture of various, comprises the formulas I and II in general

with the above

CH ₂ —C - CH ₂ - no ₂

CH ₂ - c - ch ₂ - no ₂ polymerization stage

P.

(II) (II)

Often compounds of formula (III) (IV) are present as components of formula (III) and (IV) wherein, for simplicity, a polyisobutyl radical

indicates R.

By-products can in many cases be

chit - according to the nitrogen oxides used or mixtures oxide nitrogen with the following compounds by air of of formula V to VIII O - NO I 0- I no ₂ 1 R - CH ₂ - C - CH _{2 -} NO ₂ I R 1 - CH ₂ --Ο- Ι -ch ₂ - no ₂ 1 CH3 CH (IN) (VI)

O - 0 - NO ₂ NO

R - CH ₂ - C - CH _{2 -} NO ₂ I R - CH ₂ - C - CH _{2 -} NO ₂ 1 1 ch ₃ ch ₃ (VII) (VIII)

The compounds of the formulas I to IV form the essential components of the reaction product according to the invention. Usually, the mixture of compounds of the formulas I to IV has a proportion of from 50 to 90% by weight, in particular from 60 to 85% by weight of the reaction product according to the invention. The remainder consists essentially of compounds of formulas V to VIII as well as compounds of formulas I to VIII analogous structures of formulas IX to XVI, which are based on minute amounts of the polyisobutenes present in the β-position of the double bond polyisobutenes present.

no ₂ no ₁ i 1 no ₂ 1 OH | R-CH - C - CH ₃ I . R-CH 1 - c — ch ₃ I 1 ch ₃ 1 ch ₃ (IX) (X) NO ₂ NO ₂ í 1 no ₂ OH | R - CH - C - CH ₂ - NO ₂ 1 1 R — CH - 1 - c - ch _{2 -} no ₂ I CH ₃ 1 ch ₃ (XI) (XII) NO ₂ o-NO I 1 no ₂ 1 0 - no ₂ I 1 1 R - CH - C - CH ₃ I R - CH 1 - c - ch ₃ I 1 CH ₃ 1 ch ₃ (XIII) (XIV) N0 ₂ 0 - 0 - N0 ₂ I i no ₂ 1 NO I 1 R - CH - C - CH ₃ 1 R-CH 1 - c - ch ₃ I ch ₃ 1 ch ₃ (XV) (XVI)

As a rule, the compounds of the formulas I to IV are formed in the following proportions by weight:

I 25 until 70 separately 35 until 60 % II 3 until 30 % / separately 5 until 25 % III 0 until 30 separately 5 until 25 % IV 0 until 25 separately 2 until 15

wherein the percentages refer to the amount of compounds of the formulas I to IV (sum of 100% by weight).

If the polyisobutenes employed, as mentioned above, contain other polymerizate forming units such as isobutene, the radical R in the formulas III to XVI and, by analogy, the molecular moiety in the formulas I and II have the corresponding meaning.

The invention also relates to the reaction products of the described highly reactive polyisobutenes and nitrogen oxides or mixtures of oxides of nitrogen and oxygen which have remained unreacted following their formation by elimination with bases in nitro-containing alkenes.

Suitable structures of such by-products are, in particular, the compounds of formulas XVII and XVIII,

R - CH ₂ - C = CH - NO ₂ I ch ₃ (XVII) No ₂

I

R - C = C - CH ₃ I ₃ (XVIII) wherein the compound of formula XVII originated originally from a polyisobutene with a terminal double bond and the compound of formula XVIII originated originally from a polyisobutene with a double bond at the β position. Also, compounds of formulas II, IV, X and XII may be by-products of such additionally incorporated elimination reactions. Generally, as a product of the elimination reaction, a mixture of the various substances constituting the major component in the compound of formula XVII and the compound of formula XVIII is present in only minor amounts or is absent at all.

Such elimination reactions are performed under appropriate conventional conditions. The alkali metal hydroxides such as sodium and potassium hydroxides, alkali metal alcoholates such as sodium methoxide, sodium ethoxide, sodium isopropylate or potassium tert-butyrate or, in particular, alkali metal carbonates or bicarbonates, such as potassium carbonate, are used as the base. and sodium carbonate or potassium bicarbonate.

The thus formed nitro-containing alkenes are useful as intermediates for the production of polyisobutynamines effective as additives to fuels and lubricants.

The reaction products of polyisobutenes and nitrogen oxides or mixtures of oxides of nitrogen and oxygen are used as detergents and dispersants in spark ignition fuels because of their properties. They may also find application as lubricant additives.

When the reaction products of the invention, which are nitroalkanes, are hydrogenated by conventional means to obtain the corresponding aminoalkanes, active compounds useful as fuel and lubricant additives are also obtained. In particular, such aminoalkanes have the general formulas (XIX) to (XXVI).

NH ₂

R - ch ₂ C - ch _{2 -} nh ₂

I ch ₃ (XIX)

OH

I

R — ch ₂ C — ch ₂ - nh ₂ ch ₃ (XX) nh ₂

R - CH ₂ -C-CH ₂ -NH ₂ CH ₂ - NH ₂

OH

I

R CH ₂ C CH _{2 -} NH ₂ ch ₂ —nh ₂ (XXI) (XXII) nh ₂ nh ₂

I I

R-CH - C - CH ₃

I ch ₃ nh ₂ oh

R - CH - C - CH ₃

I ch ₃ (XXIII)

ΝΗ ₂ νη ₂

R CH C CH ₂ -NH ₂

I ch ₃ nh ₂ oh

R CH C CH ₂ NH ₂

I ch ₃ (XXV)

Also, the corresponding aminoalkanes of formulas XXVII and XXVIII can be prepared from the subsequent products of formulas XVI and XVIII.

R _CH2 - - QH CH ₂ CH ₃ NH ₂ NH ₂

I

R CH CH - CH ₃ CH ₃ (XXVII) (XXVIII)

A suitable functionalization of the double bond in compounds of formula XVII and XVIII, like the addition of amines of the formula HNR ^ R ^ or the alcohols R ¹ OH or by cleavage to aldehydes and addition of amines of the

The formula HNR ^X R ^A to these aldehydes and subsequent hydrogenation are

'. available compounds of formula

R - ch ₂ - CH - CH _{2 -} NR ₁ R ₂ ch ₃ (XXIX)

XXIX to XXXIV

NR1R2

I

R - CH - CH - CH ₃

I

CH ₂ (XXX)

CH ₃

I

R - ch ₂ - c - ch ₂ - nh ₂

NRiRZ

NH ₂ NR 12

R - CH - C - CH ₃

I ch ₃ (XXXI)

NH ₂ ORi ^R - CH - c - CH ₃ I CH ₃ (XXXIV)

CH ₃

R - _CH2 --c - _CH2 --NH,

I 0R1 (XXXIII) wherein R ¹ and R ² organic group, wherein R ² can also be a hydrogen atom. Particular mention is made of an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an optionally substituted aryl group having 6 to 14 carbon atoms.

If the reaction products according to the invention are used as fuel additives, they are preferably added in an amount of 10 to 5000 ppm, in particular 50 to 1000 ppm. In the case of lubricants, as a rule, more additives are added, the additives here may represent 0.1 to 6% by weight, in particular 0.5 to 5% by weight.

If the dispersing properties of the substances according to the invention are to be used in particular, they can also be combined with known detergents as additional additives.

In principle, any known product suitable for this purpose can be used as the detergent ingredients in admixture with the substances according to the invention as dispersants (for example J. Falbre, U.Hasserodt, Uatalysatoren, Tenside und Mineraloladditive, G. Thieme Stuttgart publ. 223, 1978, or K. Owen Gasoline and Diesel Fuel Additives, John Wiley & Sons, p. 23, 1989).

Nitrogen-containing detergents are preferably used, for example compounds containing an amino or amido group. Particularly suitable are the polyisobutylamines according to European Patent Application No. EO-A 0 244 616, amides and / or imides of ethylenediaminetetraacetic acid according to European Published Application EP-A 0 356 725, with reference to the definitions contained therein. The products described in the aforementioned applications have - in accordance with the production, similar to the reaction products according to the invention - the advantage that they are free of chlorine or chlorides.

If the detergency effect of the reaction products according to the invention is to be preferably used, these substances can also be combined with oils as carriers. Such carrier oils are known, in particular polyglycol-based oils, for example the corresponding ethers and / or esters described in U.S. Pat. Nos. 5,004,478 and DE-A 38 38 918, are particularly suitable. Polyoxyalkylene monools with hydrocarbon may also be used end groups (U.S. Pat. No. 4,877,416) or carrier oils (DE-A 41 42 241).

Suitable fuels for petrol engines are normal and unleaded normal and super petrol. Petrols may also contain components other than hydrocarbons, for example alcohols such as methyl tert-butyl ether. In addition to the reaction products of the invention, the fuels generally also contain other additives, such as corrosion inhibitors, stabilizers, antioxidants and / or other detergents.

Corrosion inhibitors are mostly ammonium salts of organic carboxylic acids, which tend to form a film due to the corresponding structure of the starting materials. Corrosion inhibitors are also often used to lower the pH by amines. Heterocyclic aromatics mostly serve as corrosion protection for non-ferrous metals.

Testing the suitability of the products as fuel additives is carried out by the engine test: at the test sites according to CEC-F-04-A-87 the effect of keep clean was tested on the Opel-Kadett engine filling valves containing 1.2 liters.

The invention is illustrated, but not limited, by the following examples. Percentages are by weight except E values.

DETAILED DESCRIPTION OF THE INVENTION

Production examples

The assignment of the structures I to IV and the calculation of the mass fraction of the individual compounds of the formulas I to IV are carried out by ¹ H-NMR spectroscopy (measurement in CDCl ₃ , values in ppm):

ch ₂ - ⁿ o ₂ in I: 4.65 (D, 1H), 5.20 (D, 1H), AB-System ch ₂ -no ₂ in II: 4.35 (D, 1H), 4.50 (D, 1H), AB-System ch ₂ -no ₂ in III: 5.30 (D, 2H); 5.42 (D, 2H); AB-System ch ₂ -no ₂ in IV: 4,71- 4.74 (WITH/ 4H)

Example 1 * »’

In a flask with stirrer, 722 g of highly reactive polyisobutene (Glissopal ^R ES 3250) having an average molecular weight of 1017 and an E value of 85% and 787 g of Mihagol ^R M (a mixture of C-C13 n-paraffin) are mixed. At a heating mantle temperature of 40 ° C, 85 g (1.85 mol) of nitrogen dioxide were introduced over three hours. The temperature rises to 43 DEG C. After stripping the excess nitrogen dioxide with nitrogen, 500 g of water are added and stirring is continued for 2 hours at 50 DEG-60 DEG C. The phases are separated and the organic phase is distilled off under vacuum to remove residual water.

1515 g of a reaction solution consisting of about 52% of the reaction products are obtained. Preparative chromatography gave complete reaction. According to 1 H-NMR spectrum, the composition of the product was 52% I, 23% II, 12% III and 8% IV, based on the amount of I to IV as a whole.

Elemental analysis: 81.5% C, 14.3% H, 2.7% O, 1.0% N.

Example 2

The procedure is as in Example 1, but the reaction mixture is not treated with water but held at 40-50 ° C at 100 Pa for one hour. 1537 g of the reaction mixture are obtained.

Elemental analysis: 81.8% C, 13.4% H, 2.7% 0.1, 1.1% N. Approximately 50% of the reaction product in the reaction solution has < 1 > H-NMR: 58% I, 22% II , 12% III and 8% IV, related to the quantities I to IV as a whole.

Example 3

The procedure is as in Example 1, but 2.6 g of water are added to the reaction mixture. After heating under vacuum, 1564 g of the reaction mixture is obtained.

Elemental analysis: 81.8% C, 14.2% H, 2.7% O, 1.5% N.

According to 1 H-NMR, the reaction product contained 55% I, 24% II, 13%

I

III and 8% IV, referring to quantities I to IV as a whole.

Example 4

200 g of the highly reactive polyisobutene of Example 1 and 225 g of tert-butyl methyl ether are treated in a mixer. At 60 ° C, 30 g of nitrogen dioxide are introduced over two hours. After cooling, excess nitrogen dioxide was expelled with nitrogen and the reaction mixture was stirred with 120 g of water at 60 ° C for three hours. After phase separation, the solvent is distilled off from the organic phase in vacuo. 218 g of the reaction product are obtained.

Elemental analysis: 79.1% C, 13.0% H, 5.2% O, 2.1% N. According to ¹ H-NMR, the reaction product contains 59% I, 22% II, 12% III and 7% IV. relating to quantities I to IV as a whole.

Example 5

The procedure is as in Example 4, but nitrogen dioxide is introduced into the reaction mixture at -8 to -5 ° C. 215 g of product are obtained.

According to 1 H-NMR, the reaction product contained 52% I, 21% II, 18% III and 9% IV, based on the amount of I to IV as a whole.

Example 6

200 g of the highly reactive polyisobutene of Example 1 and 225 g of tert-butyl methyl ether are treated in a mixer. At 0 [deg.] C., 17.1 g of nitrogen monoxide are introduced over a period of two hours, to which 1: 1 by volume of air is admixed. After stirring for three hours at 20 DEG C., the mixture is mixed with 150 g of water and kept at 50 DEG to 60 DEG C. for 3 hours. After cooling, the phases are separated and the solvent is distilled off from the organic phase. 218 g of the reaction product are obtained which, according to ¹ H-NMR, contains 42% I, 10% II, 8% III and 4% IV, based on the total amount of product.

Example 7 (comparative)

720 g of polyisobutene with only a small amount of terminal double bonds (Indopol ^R H 100, average molecular weight 930, bromine number 22.4, E = 10%) and 820 g of Mihagol ^R M (n-paraffin blend with 10 up to 13 carbon atoms). 115 g of nitrogen dioxide are introduced at 40 DEG C. over four hours. After stripping the excess nitrogen with nitrogen, the reaction product is mixed with 350 g of water and stirred at 60 ° C for three hours. After phase separation, it is again mixed with water and finally the organic phase is briefly distilled under vacuum. 1570 g of product are obtained in the form of a clear liquid. Preparative chromatography showed 94% reaction of the charged polyisobutene.

Elemental analysis: 81% C, 14.1% H, 3.0% O, 1.2% N.

When the reaction is carried out with tert-butyl methyl ether and after treatment with distilling off the solvent, the product is free of solvent.

Elemental analysis: 80.0% C, 13.4% H, 4.7% O, 0.2% N. According to ¹ H-NMR, at 4.2-5.4 ppm, it provides an unstructured multiplet that cannot be assigned any defined structure.

Example 8

400 g of the reaction solution according to Example 4 are stirred, after evaporating the tert-butyl methyl ether solvent, with 600 g of water and 20 g of sodium carbonate at 25 ° C for 20 hours. To improve phase separation, the reaction mixture is mixed with 140 g of 10% hydrochloric acid. and then the upper organic phase is separated and concentrated. 197 g of the reaction product are obtained.

I

Elemental analysis: 81.6% C, 13.5% H, 3.3% O, 1.3% N.

According to ¹ H-NMR, in addition to the residues of compound II, it mainly shows compound XVII in cis- and trans- form, apparent from the two singlets at 6.9 and 7 ppm.

Examples of use:

Keep-clean-test at filling valves

Engine tests are performed on a 1.2 liter Opel Kadett engine (according to CEC-F-04-A-87).

Fuel used: unleaded petrol Euro-super Additive dosing: 200 ppm each.

Ex. no. Additive Ex. *) Deposits on the filling valve [mg] ' valve 1 valve 2 valve 3 valve 4 9 4 4 (210) 0 (150) 0 (154) 1 (200) 10 1 3 (277) 3 (175) 6 (183) 5 (337) 11 2 1 (277) 1 (175) 0 (183) 3 (337)

£) ¹ In brackets are values without additive (blank)

The results clearly show the cleaning effect of the additive of the invention.

Industrial usability

The reaction products according to the invention are used as additives for petrol engines and as lubricants additives. The additive oil according to the invention shows a significant reduction in deposits on the engine fill valves.

Claims (19)

PATENT CLAIMS A reaction product of polyisobutenes with nitrogen oxides or a mixture of oxides of nitrogen and oxygen, the polyisobutene having a medium polymerization degree of P = 10 to 100, having an E = 60 to 90% double bonds capable of reacting with maleic anhydride, the E value being 100 % corresponds to a numerical theoretical value in case each polyisobutene molecule has such a reactive double bond. 2. The reaction product according to claim 1, wherein the polyisobutene is present 20% polymerizable units 4 carbon atoms such as isobutene and / or monomer with 3 carbon atoms and / or ethylene. Reaction product according to claim 1 or 2, consisting of polyisobutenes and nitrogen oxides or mixtures of nitrogen oxide and oxygen in the form of a mixture of various nitro-containing alkanes, the mixture having as a main component the compounds of the formulas I and II N0 ₂ C — ch ₂ —NO ₂ (i) ch ₃ OH ch ₃ with degree of polymerization P. Process for the production of reaction products of polyisobutenes with nitrogen oxides or mixtures of oxides of nitrogen and oxygen according to claim 1, characterized in that the isobutenes are reacted with nitrogen oxides in a molar ratio of 1: 2 to 1: 4 at a temperature of -30 to 150 ° C. A reaction product according to claim 1 or 2, which, following its formation, is converted by alkali elimination in alkanes containing nitro groups. Reaction product according to claim 1 or 2, which, following its formation, is converted by alkali elimination in alkanes containing nitro groups of the general formula XVII and / or XVIII, R-CH ₂ -C? I ch ₃ CH - NO ₂ no ₂ R - C = C - CH _third I ch ₃ (XVII) (XVIII) wherein R represents a polyisobutyl group of the formula H3C - · c —I- ch ₂ - r1 — IA 1J CH ₃ / CH ₃ / β with a polymerization stage P as defined above. A process for the production of nitro-containing alkenes, characterized in that the reaction products of the polyisobutenes and nitrogen oxides or of the mixture of oxides of nitrogen according to claims 1 and 2 are subsequently subjected to elimination with a base to form them. The reaction product according to claim 1 or 2, which, following its formation, is converted by hydrogenation in an aminoalkane. Reaction product according to claim 1 or 2, which is subsequently modified by hydrogenation to aminoalkanes of the general formulas (XIX to XXVI). NH ₂ ^{R CH} 2 - C - CH _{2 -} NH ₂ ch ₃ (XIX) OH I R ch ₂ - c - CH ₂ —nh ₂ ch ₃ (XX) n ₂ I ^R ch ₂ - c - ch ₂ - nh ₂ ch ₂ - nh ₂ (XXI) nh ₂ nh ₂ I I R — ch — c - ch ₃ ch ₃ (XXIII) NH ₂ nh ₂ II ^R CH — C · —CH ₂ - NH ₂ ch ₃ (XXV) OH I ^R CH ₂ - C - CH _{2 -} NH ₂ CH ₂ -NH ₂ (XXII) nh ₂ oh R - CH - C - CH ₃ I ch ₃ (XXIV) NH ₂ oh I I R - ch - c - ch _{2 -} n h ₂ ch ₃ (XXVI) wherein R represents a polyisobutylene group of the formula wherein P represents the above polymerization step. Process for the production of aminoalkanes, characterized in that the reaction products of polyisobutenes and nitrogen oxides or of the mixture of oxides and oxygen according to claim 1 or 2 are hydrogenated following their formation. The reaction product according to claim 1 or 2, which, following its formation, is converted by elimination with bases in nitro-containing alkenes and subsequently hydrogenation to aminoalkanes. A reaction product according to claim 1 or 2 converted following its formation by elimination, alkali in nitro-containing alkenes and subsequent hydrogenation to aminoalkanes of formulas XXVII and / or XXVIII NH ₂ R - _CH2 --CH - _CH2 --NH ₂ R - CH - CH - CH ₃ CH ₃ CH ₃ (XXVII) (XXVIII) wherein R is a polyisobutyl radical CH ₃ / _{β 2} above characterized by the polymerization stage P. 13. Method. A process according to claim 1, characterized in that the reaction products according to claim 1 or 2 are subjected to alkali elimination following their formation. and the formed nitro-containing alkenes are hydrogenated. * The reaction product according to claim 1 or 2, which, following its formation, is converted by elimination with bases in nitro-containing alkenes, by addition of amines or. alcohols followed by hydrogenation or cleavage to aldehydes and addition of amines to these aldehydes and subsequent hydrogenation to aminoalkanes. Reaction product according to claim 1 or 2, which, following its formation, is converted by elimination with bases in nitro-containing alkenes, addition of amines of formula HNR 1 -rZ or alcohols of formula R ¹ -OH and subsequent hydrogenation or cleavage to aldehydes and addition of amines of formula HNR R to these aldehydes and subsequent hydrogenation to aminoalkanes of formulas XXIX to XXXIV R-CH ₂ - CH-CH ₂ -NR ¹ R ² CH ₃ (XXIX) CH I R - ch ₂ - c - ch ₂ - nh ₂ NR ¹ R ² (XXXI) CH I R c -CH ₂ -CH ₂ -NH ₂ OR ¹ NR ¹ R ² I R - CH - CH - CH CHj (XXX) NH ₂ NR 1 R 2 R - CH - C - CH CHj (XXXII) NH ₂ OR1 R - CH - C - CH ₃ I CH 3 (XXXIII) (XXXIV) wherein R represents a polyisobutyl group of the above-described polymerization stage P, wherein R ¹ and R ² are C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 5 -C 8 cycloalkyl, C 7 -C 18 aralkyl and optionally substituted C 6 -C 14 aryl, wherein R ² may also represent a hydrogen atom. A process for the production of aminoalkanes, characterized in that the reaction products according to claim 1 or 2 are subjected, after their formation, to base elimination and to the formed nitro-containing alkenes are added amines or alcohols and the products are hydrogenated or cleaved to aldehydes and addition amines to these aldehydes and subsequent hydrogenation are converted to aminoalkanes. Use of reaction products of polyisobutenes with nitrogen oxides or a mixture of oxides of nitrogen and oxygen according to claims 1 to 16 as additives for fuels and lubricants. 18. Diesel fuels, characterized in that they contain an effective amount of the reaction products of polyisobutenes with nitrogen oxides or with a mixture of oxides of nitrogen and oxygen according to claims 1 to 16. Lubricants, characterized in that they comprise an effective amount of the reaction products of the polyisobutenes with nitrogen oxides or with a mixture of oxides of nitrogen and oxygen according to claims 1 to 16.