DE19618270A1 - Modified long-chain poly:amine(s) combining detergent and dispersant action in fuel and lubricant - Google Patents

Abstract

Modified long-chain polyamines of formula (I), have terminal lactam group(s), in which R1 = linear or branched polyalkyl with a number average molecular weight (Mn) of 150-40000; n = 0 or 1; Z = alkylene with 3-5 carbon (C) atoms, optionally with alkyl, cycloalkyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl substituent(s); A = a group of formula (II); Alk = optionally substituted alkylene; R2 = hydrogen (H), alkyl, alkenyl, alkynyl or aryl; m = -=1-; if n = 0, X = nitrogen (N); if n = 1, X = -NH- or -NR3-; R3 = alkyl; or X-A = a chemical bond. Also claimed are lubricant and fuel compositions and additives containing compound(s) (I) and optionally other usual additives.

Description

The present invention relates to cyclic polyalkylamines vate, processes for their manufacture, and power and lubrication substances and additive concentrates, which these innovative compounds gene as additives.

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 is rich ter and the combustion becomes incomplete. As a result of it he the proportion of unburned or partially burned coals increases Hydrogen in the exhaust gas and gasoline consumption increases.

It is known that in order to avoid these disadvantages, fuel wheel additives for keeping valves and carburetor or injection clean systems are used (cf. e.g. M. Rossenbeck in Katala gates, surfactants, mineral oil additives, ed. J. Falbe, U. Hasserodt, P. 223, G. Thieme Verlag, Stuttgart 1978). Depending on the mode of action and preferred site of action of such detergent additives you two generations today. The first generation of additives could only prevent the formation of deposits in the intake system, but do not remove any existing deposits. The Second generation additives, on the other hand, can prevent deposits prevent and eliminate (keep-clean and clean-up effect). This is particularly due to their excellent thermal stability Zones of higher temperature, such as particularly at the inlet valves, enables.

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 two 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 po lymeren basic body by amines or preferably ammonia. After partly in this process the use of chlorine, which is used for As a result, products containing chlorine or chloride occur, which is no longer wanted today.

In the second process, the polyisobutylamines are based on Polyisobutene via hydroformylation and then reductive Amination according to EP 0 244 616.

Used in this second process for reductive amination If ammonia is used, the reaction products of the ammo show niaks mostly an excellent effectiveness regarding valve and Carburetor cleanliness, however, behave neutrally at most their effect as an engine lubricant, particularly with regard to their oil sludge dispersing effect.

There are particularly technical and economic advantages such additives, which also have the properties of De Combine reagents and dispersants and simplify them che, chlorine-free synthesis methods are available.

Various additives of this type are already known. So be writes e.g. B. EP 0 568 873 producible by cyanoethylation β-aminonitriles of the formula

wherein
Ra represents an aliphatic, alkyl side group-containing hydrocarbon radical with a molecular weight (number average) of 250 to 5,000 and
R ^b , R ^c and R ^d independently of one another are hydrogen or a C₁-C₈-alkyl radical or R ^b or R ^{d are} a phenyl radical, and the corresponding N-alkyl-1,3-propylene-diamines obtained by hydrogenation.

However, there is an additional need for more chlorine-free ones Additive components to meet the additive 's requirements to be able to better adapt to the respective area of application.  

The present invention is therefore based on the object other, suitable as fuel and lubricant additives, about chlorine-free synthesis accessible compounds are available too put.

It has now been found that this problem is solved by Be providing derivatives of long chain amines which can be obtained via a Functionalization of the amine group by implementation with a lac receives tone.

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

wherein
R₁ for a straight-chain or branched polyalkyl radical with a number average molecular weight of 150 to 40,000
stands,
n represents 0 or 1;
Z represents a C₃-C₅ alkylene group which is optionally substituted one or more times by alkyl, cycloalkyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl groups, A represents a group of the formula (II)

stands in what
Alk in each case represents a straight-chain or branched, optionally substituted alkylene radical,
R₂ is a hydrogen atom, an alkyl, alkenyl, or Al kinylrest or an aryl radical and
m represents an integer from 0 to 10;
and
if n is 0
X represents N; or
if n is 1
X represents -NH- or -NR₃-, wherein R₃ represents alkyl; or together with A stands for a chemical bond.

The invention also relates to compounds of the formula (III)

wherein R₁ and Z have the meanings given above.

The invention preferably relates to additives of the formula (I) or (III) wherein Z bears up to five substituents independently are selected from one another under straight-chain or branched C₁-C₁₀ alkyl, especially C₁-C₆ alkyl, phenyl or naphthyl. Be Compounds in which Z is selected from are particularly preferred the unsubstituted, straight-chain C₃-C₅ alkylene groups 1,3-Pro pylene, 1,4-butylene and 1,5-pentylene.

The polyalkyl radical R₁ in compounds of the general formula (I) or (III) is preferably obtainable by homo- or copolyme Rization of straight-chain or branched C₂-C₃₀ alkenes, wherein C₂-C₆ alkenes and in particular C₂-C₄ alkenes are preferred. Especially the preferred C₂-C₄ alkenes are 1-alkenes, such as propene, 1-butene, Isobutene. For example, R₁ from a copolymer of 1-butene and isobutene derived, wherein R₁ is also a medium Mo can have a molecular weight of about 800 to about 1500. R₁ can but can also be derived from a 1-n-alkene with 3 to 6 coals atoms and, based on the total weight of the rest R₁, 0 to about 50 wt .-% ethene, wherein R₁ about 20 to about 400 coals includes atoms.

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 for example, the following radicals can be mentioned: C₁-C₆ alkylre 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 alkyl residues, such as un branched heptyl, octyl, nonyl and decyl.

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; long 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 are obi ger C₂-C₁₀ alkenyl radicals.

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, cyclobutyl ethyl, 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 Phe nyl-C₁-C₁₀-alkyl and naphthyl-C₁-C₁₀-alkyl, the C₁-C₁₀-alkyl part 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, Byrrolyl, Imidazolyl, Pyra zolyl, oxazolyl, isoxazolyl, oxadiazolyl, tetrazolyl, pyridyl, Pyrimidinyl, pyrazinyl, pyradizinyl, triazinyl, tetrazinyl and the like.

The hetero is in the heteroarylalkyl groups according to the invention roaryl part for a heterocyclic ring as defined above, and the alkyl part is preferably a C₁-C₁₀ alkyl radical above Definition.  

Straight-chain or branched given usable according to the invention optionally substituted alkylene radicals include straight-chain ones 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-dimethylpropylene, 1-methyl-3-ethyl-pro pylene, 2,3-diznethylbutylene, 1,3-dimethylbutylene, 1,1-dimethylbu tylene, 1,2-dimethylpentylene and 1,3-dimethylhexylene.

Examples of suitable substituents according to the invention are the C₁-C₆-alkyl, C₁-C₆-alkyloxy, C₂-C₆-alkenyl, C₁-C₆-alkanoyl, such as e.g. B. acetyl and propionly, nitro and amino.

The invention also relates to a method of manufacture tion of compounds of general formula (I), wherein one Amine of formula (IV)

wherein R₁, X, A and n have the meanings given above, with a lactone of the general formula (V)

wherein Z has the meanings given above, and Product isolated.

The manufacturing method according to the invention is preferably so carried out that the polyalkylamine of formula (IV) in Sub punch or in a suitable solvent, such as. B. Tetrahy drofuran or other inert solvents, in conventional Way at elevated temperature, such as. B. about 200 to 320 ° C, and increased pressure, such as B. 50 to 300 bar with the lactone (V) sets, and the product formed with separation of the Re action formed water and possibly unreacted Lac tons wins.

Are mixtures of Lactones of the general formula (V) used, he can Additives according to the invention simultaneously have different cyclic end groups included.

The polyalkylamines of the general formula (IV) are be known starting products and can by hydroformylation reactive polyalkenes and subsequent reductive amination of the  Oxo products are manufactured. The reactive polyalkenes with egg nem average molecular weight of about 150 to 40,000, are homo- or Copolymers of straight-chain or branched C₂-C₃₀ alkenes, preferably C₂-C₆ alkenes, especially C₂-C₄ alkenes. Reactive Polyalkenes include unsaturated polymers of high chemical homo genicity, with more than 10% of the double bonds alpha-permanent are. One way to make reactive polyalkenes is disclosed in DE 27 02 604. In particular, such are reactive Polyalkenes preferred, which from 1-alkenes, such as. B. ethylene, propy len, 1-butene, isobutene or mixtures thereof.

As polyalkylamines of the general formula (IV) come also in Be traditional amines according to EP 0 244 616, EP 0 695 338 or WO 94/24231, the content of which is hereby incorporated by reference. EP 0 244 616 describes in particular those polyalklamines in which the radical R₁ is derived from isobutene and up to 20% by weight of n-butene, where the molecular weight of the polyisobutene residue is from about 300 to about 5000 can be. EP 0 695 338 and WO 94/24231 describe ben in particular those polyalkylamines in which the rest of R₁ abei tet is from one or more 1-n-alkenes with 3-6 carbon fatomen and up to 50 wt .-% ethene, with Z about 20-400 coals can have atoms of matter.

Essential criterion for all poly usable according to the invention However, alkylamine is that it has at least one primary amine group contain the derivati with a lactone as described above can be settled.

Additives starting from are particularly preferred according to the invention Polybutyl and polyisobutyl amines of the formula (IV) are prepared, which are known from EP 0 244 614.

The lactones of the formula (V) used for derivatization are also known or can in a manner known per se, such as e.g. B. with the help of Baeyer-Villingen oxidation. According to the invention, preference is given to using γ-, δ- or ε-lactones, such as B. γ-butyrolactone, γ- or δ-valerolactone or ε-caprolactam and the mono- or polysubstituted analogues thereof.

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, anti-wear 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 0.5 to 15% by weight, preferably about 1 to 10 % By weight, based on the total weight of the composition ten.

Examples of lubricants produced according to the invention include Oils and greases for motor vehicles and industrial applications 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 additives according to the invention. The connection according to the invention genes are used in particular as detergents to keep them clean of the fuel intake system. Because of their dispersing egg properties exert a positive influence on the engine lubricant that they get into during operation can.

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 Grais sage des Moteurs ", Vol. 1, 1962, page 89f. in somewhat modified ter form is described.

The additives of the invention become commercially available strength substances in a concentration of about 20 to 5000 mg / kg, preferably about 50 to 1000 mg / kg of fuel added. The invention Additional additives may also be used together with others known additives can be added.

While in lubricant compositions preferably such additives according to the invention are used, wherein R 1 is a pay has an average molecular weight of about 2000-40000 are particularly suitable for use as a fuel additive Compounds in which R₁ 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 is preferred 4,832,702 known polyisobutylamines.  

As a detergent component in the additive Ge according to the invention in principle mix any known Pro that is suitable for this products are used, such as. B. with J. Falbe, U. Hasserodt, Catalysts, surfactants and mineral oil additives, G. Thieme Verlag Stuttgart 1978, p. 221 f. or at x. Owen, Gasoline and Diesel Fuel Additives, John Wiley & Sons 1989, pp. 23 ff are.

N-containing detergents, e.g. B. Verbin that contain an amine or amide group. Especially Polyisobutylamines according to EP 0 244 616, ethylenedia are suitable mintetraacetic acid amides and / or imides according to EP 0 188 786 or Polyetheramines according to EP 0 356 725, the definitions in reference is made to these references. The described there Due to the manufacturing process, products also have the advantages part of being free of chlorine or chloride.

On the other hand, these additives can also be combined with carrier oils will. Carrier oils on polyalkylene glycol are particularly suitable base, e.g. B. corresponding ethers and / or esters, as in the US 5 004 478 or DE 38 38 918 A1 are described. Poly too oxalkylene monools with hydrocarbon end groups (US 4,877,416) or carrier oils as disclosed in DE 41 42 241 can be used.

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

example 1 Production of additives according to the invention

970 g of polyisobutylamine (prepared according to DE 36 11 230 or EP 244616) were stirred with 29.5 g of butyrolactone in an autoclave at 280 ° C. (200 bar) for 4 hours. The crude product obtained was freed from the water formed on the rotary evaporator. A slightly colored, viscous oil is obtained.
Yield: quantitative
IR (K3r) cf. Fig. 1
Characteristic bands at 1550 cm ^-1 (amide) and 3300 cm ^-1 (NH stretching vibration).

Example 2 Engine test to test the effect as an intake system cleaner

The engine tests were carried out in a Mercedes Benz X 102 E engine  CEC FO5 A 93 carried out. Fuel used: Euro-Super lead-free.

Claims (15)

1. Compound of the general formula (I) wherein
R₁ represents a straight-chain or branched polyalkyl radical with a number average molecular weight of 150 to 40,000,
n represents 0 or 1;
Z represents a C₃-C₅ alkylene group which is optionally substituted one or more times with alkyl, cycloalkyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl groups,
A for a group of formula (II) stands in what
Alk in each case represents a straight-chain or branched, optionally substituted alkylene radical,
R₂ represents a hydrogen atom, an alkyl, alkenyl or alkynyl radical or an aryl radical and
m represents an integer from 0 to 10;
and
if n is 0
X represents N; or
if n is 1
X represents -NH- or -NR ₃ -, wherein R₃ represents alkyl; or together with A stands for a chemical bond. 2. Compound according to claim 1 of the general formula (III) wherein R₁ and Z have the meanings given above. 3. A compound according to claim 1 or 2, wherein Z is one to five sub bears substituents that are independently selected under straight-chain or branched C₁-C₁₀ alkyl, phenyl or Naphthyl. 4. A compound according to any one of claims 1 to 3, wherein Z is out is chosen from unsubstituted, straight-chain C₃-C₅ alkylene groups. 5. A compound according to any one of claims 1 to 4, wherein R₁ 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 ethene, propylene, 1-butene and isobutene. 8. A compound according to claim 6, wherein R₁ is derived from poly butene or polyisobutene, or a copolymer of iso butene and up to 20% by weight of n-butene, and a medium mole Specular weight from about 800 to about 1500. 9. A compound according to claim 7, wherein R₁ is derived from one 1-n-alkene having 3 to 6 carbon atoms and, based on the Total weight of the rest R 1, 0 to about 50% by weight of ethene, wherein R₁ comprises about 20 to about 400 carbon atoms. 10. A process for the preparation of compounds of the general formula (I), characterized in that an amine of the formula (IV) wherein R₁, X, A and n have the meanings given above,
with a lactone of the general formula (V) wherein Z has the meanings given above, and the product is isolated. 11. Lubricant composition comprising in a conventional one liquid or pasty lubricant one or more ver Bonds according to one of claims 1 to 9 in a rest amount of about 1 to 15 wt .-%, based on the total weight the composition, optionally in combination with white other common lubricant additives. 12. Lubricant composition according to claim 11, comprising min at least a compound of general formula (I), wherein R₁ a number average molecular weight of about 2,000 to 40,000 having. 13. A fuel composition comprising one or more ver Bonds according to one of claims 1 to 9 in a total concentration of about 20 to 5000 mg / kg fuel, given if necessary in combination with other common fuel additives tives. 14. A fuel composition according to claim 13 comprising at least least a compound of general formula (I), wherein R₁ a number average molecular weight of about 150 to 5000 having. 15. Additive mixture for fuels or lubricants, comprising one one or more compounds according to one of claims 1 to 9, optionally in combination with other customary additives components.