DE19615404A1 - N-alkyl:formamide(s) - Google Patents

Abstract

N-alkylformamides of formula: ZCH2NY2-nHn (where, n = 0 or 1; Z = polyalkyl having no average molecular wt. of 150-40000; y = group of formula -(AlkNR1)mCOH (IIa); Alk = alkylene; R1 = H, (cyclo)alkyl, hydroxyalkyl, aminoalkyl, alkenyl, alkinyl, aryl, arylalkyl, or heteroaryl, or group of formula COH (III); in (III), Alk and/or R1 can be substituted by further alkyls carrying hydroxy or amino groups; m = 0-10; when n = 0, one Y = group of formula (IIa) and the other Y = Z-CH2 (where both Z's are same of different); when n = 0, one Y = group of formula (III) and the other Y = group of formula -AlkNR1)mAlkNR2R3 (IIb); R2 and R3 = (cyclo)alkyl, hydroxyalkyl, aminoalkyl, alkenyl, alkinyl, aryl, arylalkyl, heteroaryl or together with the N-atom form a heterocyclic ring, where R2 and/or R3 can be substituted by further alkyls carrying further hydroxy or amino groups). Production of the N-alkylformamides is also claimed. Further claimed is a lubricant composition containing 1-15 wt.% of compound (I). Also claimed is a fuel composition containing compound (I).

Description

The present invention relates to N-alkylformamides, which as Additives for fuels and lubricants are applicable, procedures for the production of these additives and fuels and lubricants as well as additive concentrates, which ent these novel additives ent hold.

Carburetors and intake systems of gasoline engines, but also injection systems for fuel metering in petrol and diesel engines are increasingly contaminated. The Impurities are caused by dust particles from the Air sucked in by the engine, unburned hydrocarbon residues out of the combustion chamber and the ventilation led into the carburetor gases from the crankcase.

These residues shift the air-fuel ratio in the Idling and in the lower part load range, so that the mixture fatter and the combustion is incomplete. As a consequence of this the proportion of unburned or partially burned coals increases Hydrogen in the exhaust gas and gasoline consumption increases.

It is known to avoid these disadvantages of fuel additives for keeping valves and carburettor or on clean spray systems are used (see e.g. M. Rossenbeck in Catalysts, surfactants, mineral oil additives, ed. J. Falbe, U. Hasserodt, p. 223, G. Thieme Verlag, Stuttgart 1978). Depending on Mode of action and preferred place of action of such detergent additives one differentiates between two generations today. The first additive Ge generation could only build up deposits in the intake system prevent, but not existing deposits again remove. The second generation additives, on the other hand, can Prevent and remove deposits (keep-clean and clean-up effect). This is particularly due to their excellent thermo stability in zones of higher temperature, such as in particular Inlet valves, allows.

The molecular construction principle of these Addi, which act as detergents tive of the second generation is based on the combination of polar Structures with mostly higher molecular weight, non-polar or oleophilic Leftovers. Typical representatives of the second generation of additives are Products based on polyisobutene in the non-polar part of the molecule, such as in particular additives of the polyisobutylamine type. Such Detergents are based on polyisobutenes after two ver different multi-stage synthesis processes can be produced.  

The first process involves chlorination of the polymer Basic body, followed by a nucleophilic substitution of the polymeric base by amines or preferably ammonia. This Variant is described for example in DE-OS 21 29 461 and 22 45 918. The disadvantage of this method is the use of Chlorine, which results in products containing chlorine or chloride occur, which is no longer desirable today.

In the second process, the polyisobutylamines are based on Polyisobutene via hydroformylation and then reductive Amination (see, for example, EP 0 244 616 and DE-OS 36 11 230) chlorine-free produced.

DE-OS 20 61 057 describes a process for the production of primary amines and corresponding formamide derivatives and Formiminoesters known in which u. a. also polyisobutylene the so-called "knight reaction" is converted to amines. The "Ritter reaction" is the implementation of olefins with HCN or Nitriles under acidic catalysis to substituted amides, which too Amines can be hydrolyzed. This reaction runs over the binding of the nitrogen atom of the cyano group to an olefin cal carbon atom and is described for example in Houben-Weyl ES, pp. 1032-1041 (1985) or Houben-Weyl, XI / 1, p. 994 f. (1957).

DE-OS 20 61 057 describes the production of polyisobutyl amine additives using the Ritter reaction. But here it is required, initially obtained through the Ritter reaction To hydrolyze formamides. The acid required for hydrolysis cannot be returned to the reaction because it is associated with the Formic acid formed during the hydrolysis is contaminated.

This creates a high degree of hydrolysis wanted acid or salt load.

EP 0 567 810 describes a process for the production of N-alkyl carboxamides are known, which also have Ritter-Reak tion are accessible. The use of these compounds as Detergents in fuels and lubricants are also featured beat. These N-alkyl carboxamides already show a good one Effect as detergents, so that hydrolysis is no longer required is harmful, and therefore no longer large quantities usable salt load accrued during their manufacture. As According to EP 0 567 810, nitrile component is preferably hydrocyanic acid turns. The yield achieved in a typical example be carries 85-90%. The use is particularly disadvantageous Formation of the toxic hydrocyanic acid in the manufacture of the additives.  

The present invention is therefore based on the object alkylamine derivatives suitable as fuel and lubricant additives to provide an improved effect regarding the valve and carburetor compliance. Furthermore should these additives be producible using a process which no longer requires the use of hydrocyanic acid, in which none larger amounts of unusable salt load more and that Products that are essentially free of acid and halogen are impurities.

It has now been found that this problem is solved by Be providing derivatives of long chain amines which can be obtained via a Receives introduction of formyl groups.

The present invention relates in particular to verbin of the general formula (I)

Z-CH₂-NY _2-n H _n (I)

wherein
n represents 0 or 1;
Z represents a straight-chain or branched polyalkyl radical with a number average molecular weight of about 150 to 40,000;
Y for a radical of the formula (IIa)

stands in what
Alk represents an alkylene radical,
R₁ represents a hydrogen atom, an alkyl, cycloalkyl, hydroxyalkyl, aminoalkyl, alkenyl, alkynyl, aryl, arylalkyl or heteroaryl radical or a radical of the formula (III)

stands,
where Alk and / or R₁ may be substituted by further hydroxyl or amino-bearing alkyl radicals, and
m represents an integer from 0 to 10; or,
when n is 0, one Y is a radical of the formula (IIa) and the other Y is Z-CH₂-, where both Z may be the same or different; or
when n is 0, one Y is a radical of the formula (III) and the other Y is a radical of the formula (IIb)

stands in what
Alk, R₁ and in the meanings given above; and
R₂ and R₃ independently represent an alkyl, cycloalkyl, hydroxyalkyl, aminoalkyl, alkenyl, alkynyl, aryl, arylalkyl or heteroaryl radical or together with the nitrogen atom to which they are attached form a heterocyclic ring, where R₂ and / or R₃ can also be substituted by further hydroxyl or amino-bearing alkyl radicals.

In particular, the invention relates to compounds of the formula (I) in which Z and n have the meanings given above, where y is a formyl radical of the formula (IIa) in which
Alk represents a C₁-C₆ alkylene radical,
R₁ represents a hydrogen atom or a C₁-C₁₀-alkyl radical, which may optionally be substituted by further hydroxy-C₁-C₆-alkyl or amino-C₁-C₆-alkyl radicals, and
m stands for an integer value from 0 to 4.

According to a further preferred embodiment, compounds of the formula (I) are provided in which Z has the meanings given above, n is 0, one Y being a radical of the formula (III) and the other Y being a radical of the formula ( IIb) where
Alk represents a C₁-C₆ alkylene radical,
R₁ represents a hydrogen atom or a C₁-C₁₀-alkyl radical which may optionally be substituted by further hydroxy-C₁-C₆-alkyl or amino-C₁-C₆-alkyl radicals,
R₂ and R₃ independently of one another are a C₁-C₁₀-alkyl radical, which may optionally be substituted by further hydroxy-C₁-C₆-alkyl or amino-C₁-C₆-alkyl radicals, and
m stands for an integer value from 0 to 4.

According to a further preferred embodiment, verbin tions of formula (IV) provided

wherein
Z has the meanings given above; and
R₄ is H or Z-CH₂-; or for a radical of the formula (IIc)

stands in what
m represents 0 or 1;
Alk represents methylene, ethylene or propylene; and
R₂ and R₃ are independently a C₁-C₆ alkyl group.

The polyalkyl radical Z is preferably obtainable by homo- or Copolymerization of straight-chain or branched C₂-C₃₀ alkene NEN, with C₂-C₆ alkenes and especially C₂-C₄ alkenes preferred are. Particularly preferred C₂-C₄ alkenes are 1-alkenes, such as propy len. 1-butene, isobutene. For example, Z can be from a copolymer be derived from 1-butene and isobutene.

Alkyl radicals which can be used according to the invention include in particular C₁-C₁₀ alkyl radicals, the straight-chain or branched, saturated Have carbon chains with 1 to 10 carbon atoms. At the following radicals can be mentioned by way of example: lower alkyl leftovers, d. H. C₁-C₆ alkyl radicals, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, i-butyl, t-butyl, n-pentyl, sec.-pentyl, i-pentyl, n-hexyl, 1-, 2- or 3-methylpentyl; longer chain term alkyl radicals, such as unbranched heptyl, octyl, nonyl and decyl and the branched analogues thereof.

In the hydroxy and aminoalkyl radicals according to the invention Alkyl part as defined above and the hydroxyl or amino group is preferably located on a terminal carbon atom.

Alkenyl radicals which can be used according to the invention comprise in particular C₂-C₁₀ alkenyl radicals which have straight-chain or branched carbon chains with at least one carbon-carbon double bond and with 2 to 10 carbon atoms. The following may be mentioned as examples of monounsaturated C₂-C₁₀ alkenyl radicals:
Vinyl, allyl, 1-propenyl, isopropenyl, 1-, 2- or 3-butenyl, methallyl, 1,1-dimethylallyl, 1-, 2-, 3-, 4- or 5-hexenyl; longer chain residues, such as unbranched heptenyl, octenyl, nonenyl and decenyl and the branched analogues thereof, where the double bond can occur in any position. According to the invention, both the cis and the trans isomers of the above C₂-C₁₀ alkenyl radical are included.

Alkynyl radicals which can be used according to the invention include in particular C₂-C₁₀ alkynyl radicals, the straight-chain or branched carbon chains with at least one carbon-carbon triple bin tion and have 2 to 10 carbon atoms. Examples include Ethynyl, 1- or 2-propynyl, 1-, 2- or 3-butynyl, as well as the corresponding alkynyl analogs of the alkenyl radicals mentioned above.

Examples of cycloalkyl groups which can be used according to the invention summarize in particular C₃-C₇ cycloalkyl, such as cyclopropyl, cyclo butyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, Cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclo butylethyl, cyclopentylethyl and the like.

Examples of aryl radicals which can be used according to the invention are phenyl and naphthyl.

Arylalkyl radicals which can be used according to the invention are in particular Phenyl-C₁-C₁₀-alkyl and naphthyl-C₁-C₁₀-alkyl, the C₁-C₁₀-Al kylteil is as defined above.

The cycloalkyl, aryl and arylalkyl used according to the invention groups can optionally 1 or more, such as. B. 1 to 4 Contain heteroatoms such as O, S and N, where oxygen and Nitrogen is preferred as the hetero atom. Examples of cyclic Heteroalkyl radicals are tetrahydrofuranyl, piperidinyl, piperazinyl and morpholinyl. Examples of heteroaryl groups are 5- or 6-membered aromatic ring systems, the 1 to 4 of the above Heteroatoms include, e.g. B. furyl, pyrrolyl, imidazolyl, Pyrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, tetrazolyl, pyri dyl, pyrimidinyl, pyrazinyl, pyradizinyl, triazinyl, tetrazinyl and the same. Heterocyclic groups of the same type with at least least a nitrogen heteroatom can be from the radicals R₂ and R₃ in the above formula (IIb), together with the nitrogen atom on the they are bound to be formed.  

Straight-chain or branched alkylene which can be used according to the invention radicals include straight-chain C₁-C₁₀ alkylene radicals, such as. B. ethylene, Propylene, butylene, pentylene and hexylene, and branched C₁-C₁₀ alkylene radicals, such as. B. 1,1-dimethylethylene, 1,3-dimethyl propylene, 1-methyl-3-ethyl-propylene, 2,3-dimethylbutylene, 1,3-dimethylbutylene, 1,1-dimethylbutylene, 1,2-dimethylpentylene and 1,3-dimethylhexylene.

Examples of suitable substituents according to the invention are C₁-C₆-alkyl, amino-C₁-C₆-alkyl, hydroxy-C₁-C₆-alkenyl, C₁-C₆-alky loxy, C₂-C₆ alkenyl, C₁-C₆ alkanoyl, such as. B. Acetyl and Propio nyl, nitro and amino.

The invention also relates to a method of manufacture tion of compounds of general formula (I), wherein one Polyalkylamine of the general formula (Va)

Z-CH₂-NA _2-n H _n (Va)

wherein
Z and n have the meanings given above,
A represents a hydrogen atom or an alkyleneimine radical of the formula (VIa)

stands,
wherein Alk and m have the meanings given above and
R₅ is defined as R₁, but does not represent a formyl group,
where, when n is 0, the two radicals A are the same or different and optionally an A is Z-CH₂-; or
a polyalkylamine of the general formula (Vb)

Z-CH₂-NXH (Vb)

wherein
Z has the meanings given above, and
X represents an alkyleneimine radical of the formula (VIb)

stands in what
Alk, R₂, R₃, R₅ and zen in the meanings given above;
reacted with carbon monoxide in the presence of an alcohol and a catalytic amount of an alkali metal alcoholate, or with an alkyl sensic acid, and the N-alkylformamide of the formula (I) isolated.

In the case of reaction with carbon monoxide, serve as a catalyst Alkali metal alcoholates. These can be heterogeneous or before trains are used as homogeneous catalysts. As an alkali metal alcoholates come e.g. B. sodium or potassium alcoholates in Consideration. The alkali metal methylates are preferably used. Sodium methylate is particularly preferred.

The reaction of the amine of formula (V) with carbon monoxide takes place preferably after setting the following parameters:

• - Carbon monoxide is used in excess in the reaction. The ratio of carbon monoxide to amine is above Partial pressure of carbon monoxide set.
• - The molar ratio of the amine to the catalytically active alka Limetal alcoholate is usually about 20,000: 1 to about 1000: 1, preferably about 12,000: 1 to about 5000: 1.
• The reaction is carried out in the presence of an alcohol, These alcohols are usually primary aliphatic C₁-C₁₀ alcohols such as methanol, ethanol, i-propa nol, n-butanol, n-pentanol and the like, preferably um Methanol or ethanol and especially methanol.
• - The reaction can be in one of the above alcohols Solvents. Can as a solvent e.g. B. are called hydrocarbons, such as hexane, cyclo hexane, C₅ to C₂₀-, such as. B. C₁₀ to C₁₃-, hydrocarbon mixtures (e.g. Mihagol), and the like. The amount the solvent is generally about 10 to 90 wt .-% based on the total batch.
• - The reaction is carried out at temperatures from about 10 to about 200 ° C, preferably at about 20 to about 100 ° C. The reaction pressure is about 10 to about 200 bar, preferably about 20 to about 100 bar. The response times are generally about 0.1 to 5 hours.

To carry out the reactions, the reactants are ver mixes and then under CO pressure to the reaction temperature brought. The workup can be carried out in a manner known per se by separating the catalyst, distilling off the solution  means and optionally chromatographic or distillative Purification of the reaction product take place.

In the case of the reaction of the amine of formula (V) with amei The following parameters preferably apply to sensic acid esters.

• - Alkyl formates are used as formic acid esters det. C₁-C₆ alkyl esters, such as. B. formic acid methyl ester and ethyl formate used; especially preferred is the methyl formate (methyl formate).
• - The molar ratio of alkyl formate, such as. B. Methyl formate to the amine is usually about 10: 1 to about 1: 1. The ester is preferably added in excess sets, e.g. B. in a ratio of about 3: 1 to about 1.3: 1.
• - The reaction can in a solvent such as. B. in one of the above solvents such as hexane, cyclohexane, C₅ to C₂₀-, such as B. C₁₀ to C₁₃, hydrocarbon mixtures (e.g. Mihagol) and the like. The amount of solvent is generally about 10 up to 90% by weight based on the total batch.
• - The reaction is carried out at temperatures from about 10 to about 200 ° C, preferably at about 20 to about 100 ° C. The reaction pressure is the intrinsic pressure of the reaction mixture at the chosen temperature. Should a higher pressure than the intrinsic pressure of the mixture may be desired, so additional Lich an inert gas such as B. nitrogen, are pressed. The reaction times are generally about 0.1 to about 5 hours.

To carry out the reactions, the reactants are ver mixes and then brought to the reaction temperature. The Workup can be carried out in a manner known per se by distillation the low-boiling components and, if necessary, by chro matographic or distillative purification of the reaction product respectively.

The reaction can be continuous or dis run continuously. The method according to the invention allows the production of the N-alkylformamides of the formula (I) with high selectivity with very good yield. Compared to that in the Method described in EP 0 567 810 via the Ritter reaction one surprisingly in the carbonylation according to the invention Yields over 95%.

The compounds of the general formula (I) according to the invention differ from those according to the prior art with the help of Compounds produced by the Ritter reaction (cf. e.g. EP 0 567 810)  u. a. characterized in that between the oligo- or polyalkyl radical Z and the amide nitrogen an additional one in the original Oligo- or polyolefin is not present methylene group, the in the production of the polyalkylamine from the reactive polyal kylene by hydroformylation and subsequent reductive amine tion is inserted.

The polyalkylamines of the general formula (V) can by hydro Formylation of reactive polyalkenes and subsequent reductive Amination of the oxo product can be produced. The reactive Polyalkenes with an average molecular weight of about 150 to 40,000 are homo- or copolymers of straight-chain or branched ten alkene monomers, each having alkyl side chains with 1 to 28, preferably have 1 to 4, particularly preferably 1 to 2 carbon atoms can. Reactive polyalkenes include higher unsaturated polymers chemical homogeneity, with more than 10% of the double bonds are alpha-constant. The production of reactive polyalkenes is e.g. B. disclosed in DE 27 02 604 or EP 0 145 235. Especially those reactive polyalkenes are preferred which consist of 1-alkenes, such as especially ethylene, propylene, 1-butene, isobutene or Ge mix of them are made.

Also come in as polyalkylamines of the general formula (V) Consider amines according to EP 0 244 616 and EP 0 695 338, on their Content hereby referred. EP 0 244 616 describes in particular those polyalkylamines in which the radical Z is derived is of isobutene and up to 20% by weight of n-butene, the molecule Lar weight of the polyisobutene residue from about 300 to about 5000 lie can. EP 0 695 338 describes such poly in particular alkylamines in which the radical Z is derived from one or more ren 1-n-alkenes with 3-6 carbon atoms and up to 50% by weight Ethene, where Z can have about 20-400 carbon atoms.

Essential criterion for all poly usable according to the invention However, alkylamine is that it has at least one primary or second contain amine group, in the manner according to the invention can be derivatized.

Additives starting from are particularly preferred according to the invention Polybutyl- and polyisobutylamines of the formula (V) prepared, the are known from EP 0 244 614. Especially preferred to use one detects polyisobutylamine with a terminal primary amino group and a molecular weight of about 800-1500.

The polyalkylamines (V) can be used as a pure substance or as a substance mixture for the preparation of the compounds according to the invention be applied. Mixtures of polyalkylamines (V) can, for example  may contain primary and secondary amines (i.e. one or two Z-CH₂ residues). In addition, the length of the polyalkyl side chain vary if a poly is used to prepare the polyalkylamine olefin mixture was used.

The amines used to prepare the polyalkylamines (V) are known connections. Examples of suitable amines include name: ammonia, ethylene-1,2-diamine, propylene-1,2-diamine, propy len-1,3-diamine, butylenediamines, the monoalkyl, dialkyl and Trialkyl derivatives of these amines, such as. B. N, N-Dimethylpropy len-1,3-diamine. Other examples are polyalkylene polyamines, de ren alkylene radicals have 1-4 linear carbon atoms, such as. B. Poly ethylene polyamines and polypropylene polyamines. Examples of poly ethylene polyamines are diethylene triamine, triethylene tetramine and Tetraethylene pentamine.

Polyamines suitable according to the invention with at least one primary Amine groups are also described, for example, in EP 0 578 323, what is hereby referred to.

Mixtures of the above amines can also be used.

The invention also relates to a lubricant composition tongues which have at least one polyalkylamine according to the invention rivat as defined above, possibly in combination with contain other common lubricant additives. examples for Common additives are corrosion inhibitors, wear protection additives tive, viscosity improvers, detergents, antioxidants, anti foaming agents, lubricity improvers and pour point compounds serer. The compounds according to the invention are usually in Amounts of about 1 to 15% by weight, preferably about 0.5 to 10 % By weight, in particular 1 to 5% by weight, based on the total weight the composition included.

Examples of lubricants produced according to the invention include Oils and greases for motor vehicles and industrial uses Drive units, such as in particular engine oils, gear oils and Turbine oils.

The invention also relates to fuel compositions such as e.g. B. Fuels for petrol and diesel engines, which invented contain polyalkylamine derivatives according to the invention. The invention ß compounds serve as detergents in particular Keeping the fuel intake system clean. Because of their disper properties exert a positive influence on the Engine lubricant in which they ran during operation can. The polyalkylamines according to the invention are commercial  usual fuels in a concentration of about 20 to 5000 mg / kg, preferably about 50 to 1000 mg / kg of fuel added. The additives according to the invention can, if appropriate, also together men can be added with other known additives.

While in lubricant compositions preferably such additives according to the invention are used, in which Z is a number has an average molecular weight of about 2000-40,000 are particularly suitable for use as a fuel additive Compounds in which Z has a number average molecular weight of about 150-5000, preferably about 500-2500, and especially which is around 800-1500.

Finally, the present invention relates to additive mixtures which in concentrated form at least one according to the invention Combination with other fuel additives, esp special detergents and dispersants. Especially be a combination with, for example, from the US 4,832,702 known polyisobutylamines. Particularly suitable the polyisobutylamines of the formula known per se R-CH₂-NR'₂, in which R is one of isobutene and 0 to 30 wt .-% n-butene derived polybutyl or polyisobutyl radical and R ′ hydrogen, C₁-C₁₀-alkyl or C₁-C₈-aminoalkyl, which is further by amino group-bearing C₁-C₆ alkyl radicals can be substituted, meaning tet.

Testing the products as fuel additives, especially on their suitability as valve and carburetor cleaner also happens With the help of engine tests, which were carried out in test bench tests with a 1.2 l Opel Kadett engine according to CEC-F-04-A-87.

The effectiveness of those obtained in the process according to the invention N-alkylformamides in intake valve maintenance are opposite the formamides described in EP 0 567 810 lower dosage (approx. 1/4 of the amount) better (see example 14).

To test the products according to the invention with regard to their Dispersant properties can be a "spot test", such as the one at game by A. Schilling in "Les Huiles pour Moteurs et la Graissge des Moteurs ", Vol. 1, 1962, page 89 f, in somewhat modified Form is described can be used.

The present invention is illustrated in the following embodiment games explained.  

Examples 1 to 13 Manufacture of polyisobutene formamide

Following one of the following general working instructions ten (A) or (B) is specified under the setting in Table 1 Process parameters polyisobutene formamide produced.

Option A)

In a 300 ml autoclave, polyisobutenamine (average mol mass = 1000, produced according to EP 0 244 616) solvent, Alcohol and sodium methylate submitted. Then the desired temperature and the carbon monoxide work pressurized. After the reaction, the reaction mixture cooled down, the autoclave relaxed, the catalyst ent distant and the solvent and excess alcohol distilled relatively separated. The remaining, colorless (and partially viscous) product is balanced. Sales and selectivity will be Determined by GC analysis (GC area%) and 1 H-NMR spectroscopy.

Variant (B)

In a 300 ml autoclave, polyisobutenamine (average mol mass = 1000, produced according to EP 0 244 616) solvents and Submitted methyl formate. Then click on the one you want Temperature heated up; this creates an inherent pressure of Reaction mixture. At the end of the reaction, the reak cooled, the autoclave relaxed and the solution medium and excess methyl formate separated by distillation. The remaining, colorless (and partially viscous) product is balanced. Turnover and selectivity become GC-analytical (GC area%) and 1 H-NMR spectroscopy.

The following table 1 gives the essential data of the reactions contrary. The turnover is based on the polyisobutenamine used. NaOMe stands for sodium methylate, MeOH for methanol, PIBA for Polyisobutenamine.

Example 14 Engine tests

The test results of an engine test (1.2 1 Opel Kadett test engine) with a polyisobutene formamide according to the invention are in fol Table 2 summarized.

Table 2

Result of the engine test

The test results of a comparable engine test (1.2 l Opel Kadett test motor) with a polyisobutene formamide according to EP 0 567 810 are summarized in Table 3 below.

Table 3

Result of an engine test

Claims (14)

1. Compounds of the general formula (I) Z-CH₂-NY _2-n H _n (I) in which
n represents 0 or 1;
Z represents a straight-chain or branched polyalkyl radical with a number average molecular weight of about 150 to 40,000;
Y for a radical of the formula (IIa) stands in what
Alk represents an alkylene radical,
R₁ represents a hydrogen atom, an alkyl, cycloalkyl, hydroxyalkyl, aminoalkyl, alkenyl, alkynyl, aryl, arylalkyl or heteroaryl radical or a radical of the formula (III) stands,
where Alk and / or R₁ can also be substituted by further hydroxyl or amino-bearing alkyl radicals, and
m represents an integer from 0 to 10; or,
when n is 0, one Y is a radical of the formula (IIa) and the other Y is Z-CH₂-, where both Z may be the same or different; or
when n is 0, one Y is a radical of the formula (III) and the other Y is a radical of the formula (IIb) stands in what
Alk, R₁ and in the meanings given above; and
R₂ and R₃ independently represent an alkyl, cyclo alkyl, hydroxyalkyl, aminoalkyl, alkenyl, alki nyl, aryl, arylalkyl or heteroaryl radical or together with the nitrogen atom to which they are attached form a heterocyclic ring, where R₂ and / or R₃ can also be substituted by further hydroxyl or amino-bearing alkyl groups. 2. A compound according to claim 1, wherein Z and n have the meanings given above, where Y is a formyl radical of the formula (IIa), in which
Alk represents a C₁-C₆ alkylene radical,
R₁ represents a hydrogen atom or a C₁-C₁₀-alkyl radical, which may optionally be substituted by further hydroxy-C₁-C₆-alkyl or amino-C₁-C₆-alkyl radicals, and
m stands for an integer value from 0 to 4. 3. A compound according to claim 1, wherein Z has the meanings given above, n is 0, one Y being a radical of the formula (III) and the other Y being a radical of the formula (IIb), in which
Alk represents a C₁-C₆ alkylene radical,
R₁ represents a hydrogen atom or a C₁-C₁₀-alkyl radical which may optionally be substituted by further hydroxy-C₁-C₆-alkyl or amino-C₁-C₆-alkyl radicals,
R₂ and R₃ independently of one another are a C₁-C₁₀-alkyl radical which may optionally be substituted by further hydroxy-C₁-C₆-alkyl or amino-C₁-C₆-alkyl radicals, and
m stands for an integer value from 0 to 4. 4. A compound according to any one of claims 1 to 3 of the formula (IV) wherein
Z has the meanings given above; and
R₄ is H or Z-CH₂-; or for a rest of the formula (IIc) stands in what
m represents 0 or 1;
Alk represents methylene, ethylene or propylene; and
R₂ and R₃ are independently a C₁-C₆ alkyl group. 5. A compound according to any one of claims 1 to 4, wherein Z is one of at least one straight-chain or branched C₂-C₃₀ alkene, preferably C₂-C₆ alkene, especially C₂-C₄ alkene or Ge mix is derived polymer residue. 6. A compound according to claim 5, wherein the alkene is a 1-alkene. 7. A compound according to claim 6, wherein the 1-alkene is selected among ethylene, propylene, 1-butene and isobutene. 8. A compound according to claim 7, wherein Z is derived from poly butene or polyisobutene, or a copolymer of iso butene and up to 20% by weight of n-butene, and an average molecule lar weight from about 800 to about 1500. 9. A process for the preparation of a compound according to any one of claims 1 to 8, wherein a polyalkylamine of the general formula (Va) Z-CH₂-NA _{2 -n} H _n (Va) wherein
Z and n have the meanings given above,
A represents a hydrogen atom or an alkyleneimine radical of the formula (VIa) stands,
wherein Alk and m have the meanings given above and R₅ is defined as R₁, but not for a myl group, where, when n is 0, the two radicals A are the same or different and, if appropriate, an A is Z-CH₂- ; or
a polyalkylamine of the general formula (Vb) Z-CH₂-NXH (Vb) wherein
Z has the meanings given above, and
X represents an alkyleneimine radical of the formula (VIb) stands in what
Alk, R₂, R₃, R₅ and zen in the meanings given above;
with carbon monoxide in the presence of an alcohol and a catalytic amount of an alkali metal alcoholate, or with an alkyl formate, and the N-alkyl formamide of the formula (I) isolated. 10. Lubricant composition containing in usual liquid or pasty lubricants one or more compounds according to one of claims 1 to 8 in a total amount of about 1-15% by weight, based on the total weight of the composition setting, possibly in combination with other übli Chen lubricant additives. 11. Lubricant composition according to claim 10, containing min at least a compound of general formula (I), wherein Z a number average molecular weight of about 2,000 to 40,000 owns. 12. A fuel composition comprising one or more ver Binding according to one of claims 1 to 8, in a total concentration of about 20 to 5000 mg / kg fuel, given if necessary in combination with other common fuel additives tives.   13. The fuel composition according to claim 12, comprising at least least a compound of general formula (I), wherein Z is a number average molecular weight of about 150 to 5000 be sits. 14. Additive mixture for fuels or lubricants, comprising one one or more compounds according to one of claims 1 to 8, optionally in combination with other customary additi ven.