WO2017009208A1

WO2017009208A1 - Use of corrosion inhibitors for fuels and lubricants

Info

Publication number: WO2017009208A1
Application number: PCT/EP2016/066229
Authority: WO
Inventors: Jochen Mezger; Markus Hansch; Marc Walter; Maxim Peretolchin
Original assignee: Basf Se
Priority date: 2015-07-15
Filing date: 2016-07-08
Publication date: 2017-01-19
Also published as: US20180251692A1; EP3322774A1

Abstract

The invention relates to novel uses of corrosion inhibitors in fuels and lubricants.

Description

USE OF CORROSION INHIBITORS FOR POWER AND LUBRICANTS

Description The present invention relates to new uses of corrosion inhibitors in fuels and lubricants.

Corrosion inhibitors are common additives in fuels and lubricants, often based on acid-containing structures, e.g. Dimer fatty acids.

A disadvantage of these corrosion inhibitors is that they tend to precipitate, especially in the presence of calcium ions, and as a result their corrosion-inhibiting action is reduced. The deposits formed by these precipitations may also affect the operation of engines, engine components or parts of the fuel system, in particular the injection system, especially the injection pumps or nozzles.

The term "injection system" is understood to mean the part of the fuel system in motor vehicles from the fuel pump through the injector outlet. In this case, the term "fuel system" is understood to mean the components of motor vehicles that are in contact with the respective fuel, preferably the area from the tank up to and including the injector outlet.

It is an embodiment of the present invention that the compounds of the invention against deposits not only act in the injection system, but also in the rest of the fuel system, in particular against deposits in fuel filters and pumps.

It was therefore an object to provide corrosion inhibitors are available, which show an increased compatibility with calcium ions and thereby retain their effect as a corrosion inhibitor. The problem is solved by the claimed use.

WO 2006/135881 describes quaternized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and an oxygen- or nitrogen-containing compound having a tertiary amino group, and subsequent quaternization by means of hydrocarbyl epoxide in combination with stoichiometric amounts of an acid, in particular acetic acid. Further quaternizing agents claimed in WO 2006/135881 are dialkyl sulfates, benzyl halides and hydrocarbyl-substituted carbonates, with dimethyl sulfate, benzyl chloride and dimethyl carbonate being investigated experimentally. None of these documents recognize the anticorrosive effect of these compounds.

WO 2014/195464 discloses the use of quaternized ammonium salts to prevent and eliminate deposits in the operation of diesel engines. Further disclosed are examples in which an anticorrosive effect of ammonium salts in metal-free die sel fuels on steel samples. Furthermore, WO 2014/195464 discloses the use of quaternized ammonium salts to reduce deposits in the intake system of a gasoline engine, in particular DISI and PFI (Port Fuel Injector) engines. According to the examples, deposits are prevented in injectors direct injection gasoline engines and previously formed deposits removed. However, WO 2014/195464 does not disclose the cleanliness of valves in intake manifold Otto engines.

Accordingly, the invention provides the use of a reaction product comprising a quaternized nitrogen compound or a fraction of a quaternized nitrogen compound obtained therefrom by purification, the reaction product being obtainable by

Reaction of a quaternizable nitrogen compound containing at least one quaternizable, in particular tertiary, amino group with a quaternizing agent which converts the at least one quaternizable, in particular tertiary, amino group into a quaternary ammonium group,

wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydro carbyl-substituted polycarboxylic acid as corrosion inhibitors in fuels having a content of alkali and / or alkaline earth metals and / or zinc of at least 0.1 ppm by weight.

The reaction products described have a particular advantage in fuels which have a content of alkali metals and / or alkaline earth metals and / or zinc of at least 0.1 ppm by weight, particularly preferably at least 0.2 ppm by weight and very particularly preferably at least 0.3 ppm by weight and in particular at least 0.5 ppm by weight. Also conceivable is a content of alkali metals and / or alkaline earth metals and / or zinc of at least 1 ppm by weight, preferably at least 2 and more preferably at least 3 ppm by weight.

Another object of the present invention is the use of a reaction product comprising a quaternized nitrogen compound or a partial fraction thereof obtained from the reaction product by purification, which contains a quaternized nitrogen compound, the reaction product being obtainable by

wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydro carbyl-substituted polycarboxylic acid as corrosion inhibitors in gasoline fuels, preferably in gasoline fuels having a content of alkali and / or alkaline earth metals and / or zinc of at least 0.1 ppm by weight have, especially preferably at least 0.2 ppm by weight and very particularly preferably at least 0.3 ppm by weight and in particular at least 0.5 ppm by weight. Also conceivable is a content of alkali metals and / or alkaline earth metals and / or zinc of at least 1 ppm by weight, preferably at least 2 and more preferably at least 3 ppm by weight.

Another object of the present invention is the use of a reaction product comprising a quaternized nitrogen compound or a partial fraction thereof obtained from the reaction product by purification, containing a quaternized nitrogen compound, the reaction product being obtainable by

wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid, in fuels, preferably in fuels which have a content of alkali and / or alkaline earth metals and / or zinc of at least 0.1 ppm by weight, particularly preferably at least 0.2 ppm by weight and very particularly preferably at least 0.3 ppm by weight and in particular at least 0.5 ppm by weight for reducing the corrosion of non-ferrous metals, especially copper and copper-containing alloys. Also conceivable is a content of alkali metals and / or alkaline earth metals and / or zinc of at least 1 ppm by weight, preferably at least 2 and more preferably at least 3 ppm by weight. It is an advantage of the reaction products described that they show their corrosion-inhibiting effect even in the presence of alkali and / or alkaline earth metals and / or zinc, preferably in the presence of alkaline earth metals. The content of alkali metals and / or alkaline earth metals in fuels is obtained, for example, by mixing with alkali metal and / or alkaline earth metal-containing lubricants, for example in the fuel pump. Furthermore, alkali and / or alkaline earth metals can originate from unsatisfactorily or insufficiently desalted fuel additives, for example carrier oils. By entraining alkali and / or alkaline earth metals in the fuels, the above-mentioned disadvantages can be caused. A source of zinc, for example, anti-wear additives. Particular examples of alkali metals are sodium and potassium, in particular sodium.

As alkaline earth metals are particularly magnesium and calcium, especially calcium.

Furthermore, zinc should be emphasized

With particular advantage, the reaction products described are still active in the presence of calcium and show no precipitation. The stated amounts of alkali and / or alkaline earth metals and / or zinc in each case relate to individual metal species.

It is a further advantage of the compounds of the invention that they increase the conductivity of fuels.

A fuel is usually a very bad electrical conductor. Thus, electrical charges tend to accumulate locally in such organic material and discharge uncontrollably as sparks, which can lead to explosions or fires upon contact of this fuel, which is naturally flammable and highly flammable, with air or oxygen. By using suitable antistatic additives, the electrical conductivity of fuels can be increased, so that static charges can no longer form and the risk of explosions and fires is reduced. Therefore, it is a further object of the present invention to use the disclosed quaternary compounds as a new and improved additive formulation suitable for antistatic and enhanced electrical conductivity of fuels, as well as for preventing electrostatic charge in chemical and physical processes, and use the described quaternary compounds to improve the electrical conductivity and to prevent electrostatic charging of fuels.

A further subject matter of the present invention is the use of a reaction product comprising a quaternized nitrogen compound or a fraction of a fraction thereof obtained by purification comprising a quaternized nitrogen compound, the reaction product being obtainable by

wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydro carbyl-substituted polycarboxylic acid, for the total or partial prevention of the formation of new deposits and / or removal of all or part of existing deposits on the fuel inlet and / or exhaust valves of gasoline engines with Port Fuel Injectors (PFI).

Deposits on the intake valves of Port Fuel Injector engines are preferably eliminated, so-called IVD (intake valve deposits).

Brief description of the invention: It has now surprisingly been found that the above object is achieved by providing quaternized nitrogen compounds, such as, for example, hydrocarbylamine compounds or fuel and lubricant compositions added thereto.

Surprisingly, the additives according to the invention, as illustrated in particular by the enclosed application examples, are surprisingly effective as corrosion inhibitors in fuels, preferably in gasoline or diesel fuels, more preferably in gasoline fuels.

Detailed Description of the Invention: A1) Specific Embodiments The present invention particularly relates to the following specific embodiments:

Use of an effective amount of at least one reaction product comprising a quaternized nitrogen compound or a partial fraction thereof obtained from the reaction product by purification, containing a quaternized nitrogen compound, the reaction product being obtainable by

Reaction of a quaternizable nitrogen compound, e.g. a quaternizable one

Alkylamine, containing at least one quaternizable, especially tertiary amino group with a quaternizing agent, which converts the at least one quaternizable, especially tertiary amino group into a quaternary ammonium group, wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid, as a corrosion inhibitor in Force or

Lubricants, preferably in fuels, more preferably in fuels having a content of alkali and / or alkaline earth metals and / or zinc of at least 0.1 ppm by weight.

Use according to embodiment 1, wherein the quaternizable nitrogen compound is selected from a) at least one alkylamine comprising at least one compound of the following general formula 3,

R _a R _b R _c N (3) where at least one of the radicals R _a , Rb and R _c , such as one or two, is a straight-chain or branched, saturated or unsaturated C 8 -C 40 -hydrocarbyl radical (in particular straight-chain or branched Cs-C ₄ o-alkyl) and the remaining radicals are identical or different, straight-chain or branched, saturated or unsaturated C 1 -C 6 -hydrocarbyl radicals (in particular C 1 -C 6 -alkyl);

b) at least one polyalkene-substituted amine containing at least one quaternizable, in particular tertiary, amino group;

c) at least one polyether-substituted amine containing at least one quaternizable, in particular tertiary, amino group; and

d) at least one reaction product of a hydrocarbyl-substituted acylating agent and a compound containing a nitrogen or oxygen atom and additionally containing at least one quaternizable, in particular tertiary, amino group; and e) mixtures thereof; or use according to embodiment 1, wherein the quaternizable nitrogen compound, e.g. is an alkylamine comprising at least one compound represented by the following general formula 3,

RaRbRcN (3) wherein all radicals R _a , Rb and R _{c are} identical or different straight-chain or branched, saturated or unsaturated C 8 -C ₄ o-hydrocarbyl radicals, in particular straight-chain or branched Cs - C ₄ o-alkyl radicals. Use according to one of embodiments 1 and 2, wherein the quaternizing agent comprises an epoxide of the general formula 4

in which

the radicals Rd contained therein are the same or different and are H or a hydrocarbyl radical, where the hydrocarbyl radical is an aliphatic or aromatic radical having at least 1 to 10 carbon atoms 4. Use according to any one of embodiments 1 to 3, wherein the free acid of the quaternizing agent is a hydrocarbyl-substituted C3-C28 dicarboxylic acid.

Use according to any of embodiments 1 to 4, wherein the hydrocarbyl substituent of the carboxylic acid is a polyalkylene radical having a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25.

Use according to one of the preceding embodiments, wherein the quaternizable tertiary amine is a compound of the formula 3 in which at least two of the radicals R _a , Rb and R _{c are} identical or different and represent a straight-chain or branched, Cio-C2o-alkyl radical and the remainder is C 1 -C ₄ -alkyl.

Use according to one of the preceding embodiments, wherein the quaternizing agent is selected from lower alkylene oxides in combination with a hydrocarbyl-substituted polycarboxylic acid.

Use according to one of the preceding embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels, and alkanol-containing gasoline fuels, such as bioethanol-containing fuels, in particular gasoline fuels.

The term "partial fraction" is preferably understood to mean that the reaction product is freed or depleted of unreacted educts, especially hydrocarbyl epoxide, and optionally byproducts, the quaternized nitrogen compound and hydrocarbyl-substituted polycarboxylic acid remaining at least partially together in the partial fraction.

In one embodiment of the present invention, the use of the quaternized nitrogen compound-containing reaction product over the use of the partial fraction obtained by purification thereof is preferred.

Respective suitable test methods for checking the above-mentioned applications are known to those skilled in the art, or in the following experimental part, which is hereby expressly incorporated by reference, described.

A2) General definitions

Unless otherwise indicated, the following general meanings apply: "Quaternizable" nitrogen groups or amino groups include in particular primary, secondary and, above all, tertiary amino groups. "Hydrocarbyl" is to be interpreted broadly and includes both long-chain and short-chain, straight or branched hydrocarbon radicals having 1 to 50 carbon atoms, which may additionally contain heteroatoms, such as For example, O, N, NH, S, may contain in their chain. A particular group of hydrocarbyl radicals includes both long and short chain, straight chain or branched alkyl radicals having 1 to 1000, 3 to 500, 4 to 400 carbon atoms.

"Long-chain" or "high molecular weight" hydrocarbyl radicals represent straight-chain or branched hydrocarbon radicals and have 7 to 50 or 8 to 50 or 8 to 40 or 10 to 20 carbon atoms, which may additionally contain heteroatoms, such as. O, N, NH, S, may be included in their chain. Furthermore, the radicals may be monounsaturated or polyunsaturated and one or more non-cumulated, e.g. 1 to 5, such as 1, 2 or 3 C-C double bonds or C-C triple bonds, in particular 1, 2 or 3 double bonds. They can be natural or synthetic.

They may also have a number-average molecular weight (M _n ) of from 85 to 20,000, such as 1 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500 In particular, they are composed essentially of C 2-6, in particular C 2-4, monomer units such as ethylene, propylene, n- or isobutylene or mixtures thereof, it being possible for the various monomers to be randomly distributed or incorporated in polymerized form as blocks. Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or poly-C2-6 or poly-C2-4-alkylene radicals. Suitable long-chain hydrocarbyl radicals and their preparation are also described, for example, in WO2006 / 135881 and the literature cited therein.

Examples of particularly useful polyalkylene radicals are polyisobutenyl radicals derived from so-called "highly reactive" polyisobutenes, which are distinguished by a high content of terminal double bonds. Terminal arranged double bonds are alpha-olefinic double bonds of the type

polymer

which together are also referred to as vinylidene double bonds. Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, in particular greater than 80 mol% or greater than 85 mol%. Particular preference is given to polyisobutenes which have uniform polymer skeletons. Uniform polymer skeletons have, in particular, those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and more preferably at least 95% by weight, of isobutene units. Preferably, such highly reactive polyisobutenes have a number average molecular weight in the range mentioned above. In addition, the highly reactive polyisobutenes can have a polydispersity in the range from 1:05 to 7, in particular from about 1.1 to 2.5, such as, for example, less than 1, 9 or less than 1.5. By polydispersity is meant the quotient of weight average molecular weight Mw divided by the number average molecular weight Mn.

Particularly suitable highly reactive polyisobutenes are e.g. the Glissopal grades of BASF SE, in particular Glissopal 1000 (Mn = 1000), Glissopal V 33 (Mn = 550) and Glissopal 2300 (Mn = 2300) and mixtures thereof. Other number-average molecular weights can be adjusted in a manner known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes of specific molecular weight ranges.

A particular group of long chain hydrocarbyl radicals includes straight chain or branched alkyl radicals ("long chain" alkyl radicals ") of 8 to 50, such as 8 to 40 or 8 to 30 or 10 to 20 carbon atoms. Another group of special long-chain hydrocarbyl radicals comprises polyalkylene radicals which are in particular composed essentially of C 2 - 6, in particular C 2-4 monomer units, such as ethylene, propylene, n- or isobutylene or mixtures thereof and have a degree of polymerization of from 2 to 100, or "3 to 50 or 4 to 25.""Short-chainhydrocarbyl" or "low-molecular hydrocarbyl" in particular represents straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, such as, for example, 2, 3 or 4 heteroatom groups, such as -O- or -NH-. or optionally mono- or polysubstituted, such as 2, 3 or 4-times substituted. "Hydrocarbylene" denotes straight-chain or mono- or polysubstituted bridging groups having 1 to 10 carbon atoms, optionally interrupted by one or more, for example 2, 3 or 4 heteroatom groups, such as -O- or -NH-. or optionally mono- or polysubstituted, such as 2, 3 or 4-times substituted.

"Alkyl" or "lower alkyl" in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 5, 1 to 6, or 1 to 7, carbon atoms, such as. Methyl, ethyl, n -propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; and n-heptyl, as well as the mono- or polysubstituted analogs thereof.

"Long-chain alkyl" denotes, for example, saturated, straight-chain or branched hydrocarbon radicals having 8 to 50, such as, for example, 8 to 40 or 8 to 30 or 10 to 20 carbon atoms, such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Pentadecyl, hexadecyl, hepadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, constitutional isomers, especially one or more branched isomers and higher homologs thereof.

"Hydroxyalkyl" is in particular the mono- or polysubstituted, in particular simply hydroxylated, analogs of the above-mentioned alkyl radicals, for example the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, for example the linear hydroxyalkyl groups, for example those having a primary (terminal) hydroxyl group, such as hydroxymethyl , 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, or those having non-terminal hydroxyl groups, such as 1-hydroxyethyl, 1- or 2-hydroxypropyl, 1- or 2-hydroxybutyl or 1-, 2- or 3-hydroxybutyl.

"Alkenyl" is mono- or polysubstituted, in particular monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, or 2 to 7 carbon atoms and a double bond in any position, for example C 2 -C 6 Alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2 -propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl , 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 , 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2 Hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl 3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl 2-butenyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl,

1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl,

1,3-dimethyl-2-butenyl 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2.3-dimethyl-3- butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,

1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.

"Hydroxyalkenyl" stands in particular for the mono- or polysubstituted, in particular simply hydroxylated, analogs of the above alkenyl radicals

"Aminoalkyl" and "aminoalkenyl" are in particular the mono- or polysubstituted, in particular simply aminated, analogs of the above alkyl or alkenyl radicals, or analogs of the above hydroxyalkyl, where the OH group has been replaced by an amino group. "Alkylene" stands for straight-chain or mono- or poly-branched hydrocarbon bridging groups having 1 to 10 carbon atoms, such as, for example, C 1 -C ₇ -alkylene groups selected from -CH ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) 3 -, - (CH ₂ ) 4-, - (CH ₂ ) ₂ -CH (CH ₃ ) -, -CH ₂ -CH (CH ₃ ) -CH ₂ -, (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ , - (CH ₂ ) ₇ -, -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) - or -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) - or C 1 -C ₄ -alkylene groups selected from -CH ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - ( CH ₂ ) ₂ - CH (CH ₃ ) -, -CH ₂ -CH (CH ₃ ) -CH ₂ - or for C ₂ -C 6 -alkylene groups, such as

-CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -, -CH ₂ -C (CH ₃ ) ₂ -,

-C (CH ₃ ) ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -C (CH ₃ ) ₂ -, -CH ₂ -CH (Et) -, -CH (CH ₂ CH ₃ ) -CH ₂ -,

-CH (CH ₂ CH ₃ ) -CH (CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) ₂ -CH ₂ -, -CH ₂ -C (CH ₂ CH ₃ ) ₂ -,

-CH ₂ -CH (n-propyl) -, -CH (n-propyl) -CH ₂ -, -CH (n-propyl) -CH (CH ₃ ) -, -CH ₂ -CH (n-butyl) - .

-CH (n-butyl) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₂ CH ₃ ) -, -CH (CH ₃ ) -CH (n-propyl) -, -CH (CH ₂ CH ₃ ) -CH (CH ₃ ) -, -CH (CH ₃ ) -CH (CH ₂ CH ₃ ) -, or for C ₂ -C ₄ -alkylene groups, for example selected from - (CH ₂ ) ₂ -, - CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -, -CH ₂ -C (CH ₃ ) ₂ -, -CH ₂ - CH (CH ₂ CH ₃ ) -, -CH (CH ₂ CH ₃ ) -CH ₂ -.

"Oxyalkylene radicals correspond to the definition of the above straight-chain or mono- or polysubstituted alkylene radicals having 2 to 10 carbon atoms, the coal chain being replaced by an oxygen radical. heteroatom 1 or more times, in particular 1-fold is interrupted. Nonlimiting examples include: -CH ₂ -O-CH ₂ -, - (CH ₂ ) 2-0- (CH ₂ ) 2-, - (CH ₂ ) 3-0- (CH ₂ ) 3-, or -CH ₂ -O- (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₃ -, -CH ₂ -O- (CH ₂ ) ₃ "aminoalkylene" correspond to the definition of the above straight-chain or a - or multi-branched alkylene radicals having 2 to 10 carbon atoms, wherein the coal chain is interrupted by a nitrogen group (in particular -NH group) 1 or more times, in particular 1-fold. Nonlimiting examples include: -CH ₂ -NH-CH ₂ -, - (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ -, or -CH ₂ -NH- (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -, -CH ₂ -NH- (CH ₂ ) ₃ .

"Alkenylene" is the mono- or polysubstituted, especially monounsaturated, analogs of the above alkylene groups having 2 to 10 carbon atoms, in particular C ₂ -C ₇ -alkenylenes or C ₂ -C ₄ -alkenylene, such as -CH = CH-, -CH = CH-CH ₂ -, - CH ₂ -CH = CH-,

-CH = CH-CH ₂ -CH ₂ -, -CH ₂ -CH = CH-CH ₂ -, -CH ₂ -CH ₂ -CH = CH-, -CH (CH ₃ ) -CH = CH-,

-CH ₂ -C (CH ₃ ) = CH-.

- "cycloalkyl" means carbocyclic radicals of 3 to 20 carbon atoms, such as C ₃ -C ₂ - cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Cy clononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl , Cyclohexyl, cycloheptyl, and cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl-methyl, cyclobutyl-ethyl, cyclopentyl-methyl, cyclopentyl-ethyl, cyclohexyl-methyl or C ₃ -C ₇ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cycloheptyl, cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl-methyl, cyclopentyl-ethyl, cyclohexyl-methyl, wherein the attachment to the rest of the molecule can take place via any suitable carbon atom.

"Cycloalkenyl" or mono- or polyunsaturated cycloalkyl "in particular represents monocyclic, mono- or polyunsaturated hydrocarbon groups having 5 to 8, preferably up to 6 carbon ring members, such as e.g. the monounsaturated radicals cyclopenten-1-yl, cyclopent-3-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl;

"Aryl" is mononuclear or polynuclear, preferably mono- or binuclear, optionally substituted aromatic radicals having 6 to 20, such as 6 to 10 ring carbon atoms, such as phenyl, biphenyl, naphthyl, such as 1- or 2-naphthyl, tetrahydronaphthyl, Fluorenyl, indenyl and phenanthrenyl These aryl radicals may optionally carry 1, 2, 3, 4, 5 or 6 identical or different substituents. "Alkylaryl" is the one or more in any position ring, especially 1- or 2-fold, alkyl-substituted analogs of the above aryl radicals, wherein aryl also has the meanings given above, such as Ci-C4-alkyl-phenyl, wherein The Ci-C4-alkyl radicals may be in any ring position.

"Substituents" for radicals specified herein are, in particular, unless otherwise specified, selected from keto groups, -COOH, -COO-alkyl, -OH, -SH, -CN, amino, -NO 2, alkyl, or alkenyl groups. "Mn" represents the number average molecular weight and is determined in a conventional manner; in particular, such data refer to Mn values determined by relative methods such as gel permeation chromatography with THF as the eluent and polystyrene standards or absolute methods such as vapor phase osmometry using toluene as a solvent.

"Mw" represents the weight-average molecular weight and is determined in a conventional manner, in particular, such data refer to Mw values determined by relative methods such as gel permeation chromatography with THF as eluent and polystyrene standards or absolute methods such as light scattering.

The "degree of polymerization" usually refers to the numerical average degree of polymerization (determination method gel permeation chromatography with THF as eluent and polystyrene standards, or GC-MS coupling) A3) Quaternizable nitrogen compounds

Quaternizable nitrogen compounds are in particular: A3.1) tertiary amines

Tertiary amines are especially compounds of the above formula (3) and are compounds known per se, e.g. described in EP-A-2 033 945.

The tertiary amine starting material (3) preferably carries a segment of the formula NR _a R b where one of the radicals has one alkyl group with 8 to 40 carbon atoms and the other an alkyl group with up to 40, particularly preferably 8 to 40 carbon atoms. The radical R _c is in particular in particular a short-chain C 1 -C 6 -alkyl radical, such as a methyl, ethyl or propyl group. R _a and Rb may be straight-chain or branched, and / or may be the same or different. For example, R _a and Rb may be a straight-chain C 12-24 alkyl group. Alternatively, only one of the two radicals may be long-chain (eg having from 8 to 40 carbon atoms) and the other may be a methyl, ethyl or propyl group.

Conveniently, the segment NR _a Rb is derived from a secondary amine, such as dioctadecylamine, di-cocoamine, dihydrogenated tallowamine and methylbehenylamine. Amine compounds, such as those available from natural materials, are also suitable. For example, a secondary hydrogenated tallow amine wherein the alkyl groups are derived from hydrogenated tallow fat and have about 4 wt% Cu, 31 wt% Ci6, and 59 wt% cis-alkyl groups. Corresponding tertiary amines of the formula (3) are sold, for example, by Akzo Nobel under the name Armeen® M2HT or Armeen® M2C.

However, the tertiary amine starting material (3) can also be formed such that the radicals R _a , Rb and R _{c have the} same or different long-chain alkyl radicals, in particular straight-chain or branched alkyl groups having 8 to 40 carbon atoms.

However, the tertiary amine starting material (3) can also be formed such that the radicals R _a , Rb and R _{c are} identical or different short-chain alkyl radicals, in particular straight-chain or branched alkyl groups having 1 to 7 or in particular 1 to 4 carbon atoms.

Further nonlimiting examples of suitable amines are: N, N-dimethyl-N- (2-ethylhexyl) amine, N, N-dimethyl-N- (2-propylheptyl) amine, dodecyldimethylamine, hexadecyldimethylamine, oleyldimethylamine, stearyldimethylamine, heptadecyldi- methylamine, cocoyldimethylamine, dicocoylmethylamine, tallow fatty dimethylamine, ditallow fatty methylamine, tridodecylamine, trihexadecylamine, trioctadecylamine, soyadimethylamine, tris (2-ethylhexyl) amine, and Alamine 336 (tri-n-octylamine).

Nonlimiting examples of short-chain tertiary amines are: trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, ethyldimethylamine, dimethylethylamine, n- Propyldimethylamine, isopropyldimethylamine, n-propyldiethylamine, isopropyldiethylamine, n-butyldimethylamine. n-butyldiethylamine, n-butyldipropylamine. Short-chain triamines are particularly useful even when the quaternizing agent (see below) carries one or more alkyl radicals Rd with more than one carbon atom or one or more aromatic radicals Rd A3.2) Quaternizable, polyether-substituted amine containing at least one quaternizable, in particular tertiary, amino group;

Such compounds are e.g. described in WO2013 / 064689 of the Applicant, to which reference is hereby expressly made.

Such substituted amines in particular have at least one, in particular a polyether substituent with monomer units of the general formula Ic

- [- CH (R ₃ ) -CH (R ₄ ) -O -] - (Ic) where

Rs and R ₄ are identical or different and are H, alkyl, alkylaryl or aryl. The polyether-substituted amine may have a number average molecular weight in the range of 500 to 5000, in particular 800 to 3000 or 900 to 1500.

The quaternizable, polyether-substituted amines are in particular nitrogen compound of the general formula Ia-1 or Ib-2

(NAO R.KR ^ ^ CH ^ -CHiFy-O- ^ H (la-1) RO ^ CH (R ₃₎ -CH (R ₄₎ -0 ^ - ₁ CH (R ₃₎ -CH (R ₄₎ -N (R ₁ ) (R ₂ ) (Ib-2)

wherein

R 1 and R 2 are the same or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together represent alkylene, oxyalkylene or aminoalkylene;

Rs and R ₄ are identical or different and are H, alkyl, alkylaryl, or aryl; R 6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom;

A is a straight-chain or branched alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S; and

n is an integer value of 1 to 50;

Particular mention should be made of those nitrogen compounds of the formulas Ia-1 and Ib-2 in which R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkenyl, or amino Ci-C6-alkyl, or R1 and R2 together form a C2-C6-alkylene, C2-C6-oxyalkylene or C2-C6-aminoalkylene radical;

Rs and R ₄ are identical or different and represent H, Ci-C6 alkyl or phenyl;

R6 is d-C20 alkyl, e.g. C10-C20, Cn-C2o or Ci2-C2o-alkyl or aryl or alkylaryl, wherein alkyl is in particular C1-C20- stands;

A is a straight-chain or branched C 2 -C 6 -alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S; and

n for an integer value from 1 to 30.

Particular mention should be made of reaction products of Ν, Ν-dimethylethanolamine and propylene oxide as described in Synthesis Example 1 of WO 2013/064689. This reaction may also be carried out uncatalyzed or with an amine (for example imidazole) as a catalyst, e.g. in M. Lonescu, Chemistry and Technology of Polyols for Polyurethanes, 2005, ISBN 978-85957-501-7. Nitrogen compounds of general formula Ia-1, can be prepared wherein

an aminoalkanol of the general formula II

(F ^ KFyN A-OH (II) wherein

R 1, R 2 and A have the meanings given above,

with an epoxide of the general formula III

O

/ (III)

(R ₃ ) HC CH (R ₄ )

wherein

R ₃ and R _{4 have} the meanings given above,

alkoxylated to give an alkoxylated amine of the formula (R ^ R ^ NAO ^ CH ^ -CHtRJ-O- ^ H (la-1) is obtained, wherein Ri to R ₄ , A and n have the meanings given above.

Nitrogen compounds of the general formula Ia-2, can be prepared wherein

where you are

an alcohol of the general formula V Re-OH (V) wherein

R6 has the meanings given above, with an epoxide of the general formula III

O

/ (III)

(R ₃₎ HC CH (R, wherein

R ₃ and R _{4 have} the meanings given above, alkoxylated to give a polyether of formula Ib-1;

R- O ^ CH ^ -CHtRJ-O ^^ CH ^ -CH ^ OH (Ib-1); wherein R3, _R4 and R6, A and n have the meanings given above

and

b) subsequently the polyether of the formula Ib-1 thus obtained with an amine of the general formula

in which R1 and R2 have the meanings given above,

aminated to obtain an amine of the formula Ib-2.

Starting compounds for the preparation of the above polyether-substituted, quaternizable nitrogen compounds are thus: 1) alcohols such as the general formula V

Re-OH (V) where R _{6 is} alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom; and

2) aminoalkanols, e.g. the general formula II

(F ^ XFyN A-OH (II)

wherein

R 1 and R ₂ are the same or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R ₂ together represent alkylene, oxyalkylene or aminoalkylene; and

A is a straight-chain or branched alkylene or alkenylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S; Other suitable groups of quaternizable aminoalcohols are compounds selected from hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group and at least one hydroxyl group which is attachable to a polyether radical. In particular, the quaternizable nitrogen compound is selected from hydroxyalkyl substituted primary, secondary, and especially tertiary monoamines and hydroxyalkyl substituted primary, secondary and especially tertiary diamines.

Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those endowed with at least one, such as 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents. Ala examples of "hydroxyalkyl-substituted monoamines" may be mentioned: N-hydroxyalkyl-monoamines, Ν, Ν-dihydroxyalkyl-monoamines and Ν, Ν, Ν-trihydroxyalkyl-monoamines, wherein the hydroxyalkyl groups are the same or different and are also as defined above In this case, hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.

For example, the following "hydroxyalkyl-substituted polyamines" and especially "hydroxyalkyl-substituted diamines" may be mentioned: (N-hydroxyalkyl) -alkylenediamines, N, N-dihydroxyalkylalkylenediamines wherein the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; Alkylene stands in particular for ethylene len, propylene or butylene.

The following quaternizable nitrogen compounds may be mentioned in particular:

4-diethylamino-1-butanol

For the preparation of the polyether-substituted quaternizable compounds (la-1 and lb-1), the following procedure can be followed: a1) starting from amino alcohols of the formula II:

The amino alcohols of the general formula II can be alkoxylated in a manner known in principle to give alkoxylated amines of the general formula Ia-1.

The carrying out of alkoxylations is known in principle to the person skilled in the art. It is also known to the person skilled in the art that the reaction conditions, in particular the choice of catalyst, can influence the molecular weight distribution of the alkoxylates. For the alkoxylation, C 2 -C 6 -alkylene oxides are used, for example ethylene oxide, propylene oxide or butylene oxide. Preference is given in each case to the 1, 2-alkylene oxides.

The alkoxylation may be a base-catalyzed alkoxylation. For this purpose, the amino alcohols (II) can be mixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide or with alkali metal alkoxides such as sodium methylate. By reducing the pressure (for example <100 mbar) and / or increasing the temperature (30 to 150 ° C), water still present in the mixture can be withdrawn. The alcohol is then present as the corresponding alkoxide. It is then rendered inert with inert gas (for example nitrogen) and the alkylene oxide (s) at temperatures of 60 to 180 ° C to a pressure of max. 10 bar added gradually. At the end of the reaction, the catalyst can be neutralized by the addition of acid (e.g., acetic acid or phosphoric acid) and filtered off as needed. However, the basic catalyst can also be neutralized by adding commercial Mg silicates, which are then filtered off. Optionally, the alkoxylation can also be carried out in the presence of a solvent. This can e.g. Toluene, xylene, dimethylformamide or ethylene carbonate.

However, the alkoxylation of the amino alcohols can also be carried out by other methods, for example by acid-catalyzed alkoxylation. Furthermore, for example Doppelhydroxidtone as described in DE 43 25 237 A1 are used, or it can double metal cyanide catalysts (DMC catalysts) can be used. Suitable DMC catalysts are disclosed, for example, in DE 102 43 361 A1, in particular in sections [0029] to [0041], and in the literature cited therein. For example, catalysts of the Zn-Co type can be used. To carry out the reaction, the aminoalcohol can be admixed with the catalyst, the mixture can be dehydrated as described above and reacted with the alkylene oxides as described. It is usually not more than 1000 ppm catalyst used with respect to the mixture, and the catalyst can remain in the product due to this small amount. The amount of catalyst can typically be less than 1000 ppm, for example 250 ppm and less.

The alkoxylation can alternatively also be carried out by reaction of the compounds (IV) and (V) with cyclic carbonates such as, for example, ethylene carbonate. a2) starting from alkanols of the formula V:

As described under the previous section a1) for amino alcohols (II), it is likewise possible analogously to alkoxylate alkanols ReOH in a manner known in principle to give polyethers (Ib-1). The polyethers thus obtained can then by reductive amination with ammonia, primary amines or secondary amines (VII) by conventional methods in continuous or batch processes using customary hydrogenation or amination catalysts such as those, the catalytically active ingredients on Basis of the elements Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Re, Al, Si, Ti, Zr, Nb, Mg, Zn, Ag, Au, Os, Ir, Cr, Mo ,, W or Combinations of these elements with one another, are reacted in conventional amounts to the corresponding polyetheramines (lb-2). The reaction can be carried out without solvent or at high polyether viscosities in the presence of a solvent, preferably in the presence of branched aliphatics such as isododecane. The amine component (VII) is generally used in excess, for example in 2 to 100 times the excess, preferably 10 to 80 times the excess. The reaction is carried out at pressures of 10 to 600 bar over a period of 10 minutes to 10 hours. After cooling, the catalyst is separated by filtration, excess amine component (VII) is evaporated off and the reaction water is distilled off azeotropically or under a gentle stream of nitrogen. If the resulting polyetheramine (Ib-2) have primary or secondary amine functionalities (Ri and / or R2 is H), this can subsequently be converted into a polyether amine having a tertiary amine function (R1 and R2 not equal to H). The alkylation can in principle be be known way by reaction with alkylating agents. In principle, all alkylating agents such as, for example, alkyl halides, alkylaryl halides, dialkyl sulfates, alkylene oxides, if appropriate in combination with acid, are suitable; aliphatic or aromatic carboxylic acid esters, in particular dialkylcarboxylates; alkanoates; cyclic nonaromatic or aromatic carboxylic acid esters; dialkyl; and mixtures thereof. The reactions to tertiary polyetheramine can also take place by reductive amination by reaction with a carbonyl compound such as formaldehyde in the presence of a reducing agent. Suitable reducing agents are formic acid or hydrogen in the presence of a suitable heterogeneous or homogeneous hydrogenation catalyst. The reactions can be carried out without solvent or in the presence of solvents. Suitable solvents are, for example, H 2 O, alkanols, such as methanol or ethanol, or 2-ethylhexanol, aromatic solvents, such as toluene, xylene or solvent mixtures of the Solvesso series, or aliphatic solvents, in particular mixtures of branched aliphatic solvents. The reactions are carried out at temperatures of 10 ° C to 300 ° C at pressures of 1 to 600 bar over a period of 10 minutes to 10 hours. The reducing agent is used at least stoichiometrically, preferably in excess, in particular in a 2- to 10-fold excess.

The reaction product thus formed (polyetheramine Ib-1 or Ib-2) can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification.

A3.3) Polyalkene-substituted amines having at least one tertiary, quaternizable nitrogen group

Also suitable as quaternizable nitrogen compounds are polyalkene-substituted amines having at least one tertiary nitrogen group. This linking group is also known and e.g. described in WO 2008/060888 or US 2008/01 13890 and the further prior art mentioned therein, to which reference is hereby expressly made.

Such polyalkene-substituted amines having at least one tertiary amino group can be derived from an olefin polymer and an amine such as ammonia, monoamines, polyamines or mixtures thereof. They can be prepared by a variety of methods, such as the following exemplified methods: One method of making a polyalkene-substituted amine involves reacting a halogenated olefin polymer with an amine as described in U.S. Patents 3,275,554, 3,438,757, 3,454,555, 3,565,804, 3,755,433, and 3,822,289. Another method for preparing a polyalkene-substituted amine involves reacting a hydroformylated olefin with a polyamine and hydrogenating the reaction product as described in US 5,567,845 and 5,496,383

Another method of preparing a polyalkene-substituted amine involves reacting a polyalkene using a conventional epoxidation reagent, with or without a catalyst, into the corresponding epoxide and reacting the epoxide to the polyalkene-substituted amine by reaction with ammonia or an amine among them Reductive animation conditions as described in US 5,350,429. Another method of preparing polyalkene-substituted amine involves the hydrogenation of a β-aminonitrile prepared by reacting an amine with a nitrile, as described in US 5,492,641.

Another method for preparing a polyalkene-substituted amine involves hydroformylating a polybutene or polyisobutylene with a catalyst such as rhodium or cobalt in the presence of CO and hydrogen at elevated pressures and temperatures, as described in US 4,832,702.

In one embodiment of the invention, the polyalkenes used for the preparation are derived from olefin polymers. The olefin polymers may include homopolymers and copolymers of polymerizable olefin monomers having 2 to about 16 carbon atoms, 2 to about 6 carbon atoms, or 2 to about 4 carbon atoms.

Interpolymers are those in which two or more olefin monomers are interpolymerized by known conventional techniques to form polyalkenes having units within their structure derived from each of the two or more olefin monomers. Thus, "interpolymers" include copolymers, terpolymers and tetrapolymers.

"Polyalkenes" from which the polyalkene-substituted amines are derived are conventionally often referred to as "polyolefins". The olefin monomers from which the olefin polymers are derived are polymerizable olefin monomers having one or more ethylenically unsaturated groups (ie,> C = C <), that is, they are monoolefinic monomers such as ethylene, propylene, 1-butene, isobutene (2-methyl-1-butene), 1-octene or polyolefinic monomers (usually diolefinic monomers) such as 1, 3-butadiene and isoprene.

The olefin monomers are usually polymerizable terminal olefins, that is, olefins having in their structure the group> C = CH 2. However, it is also possible to use polymerizable internal olefin monomers which are characterized by groups of the formula> C-C =C-C <

Specific examples of terminal and internal olefin monomers that can be used to prepare the polyalkenes by conventional methods are: ethylene, propylene, the butenes (butylene), especially 1-butene, 2-butene, and isobutylene, 1-pentene, 1- Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 2-pentene, propylene tetramer, diisobutylene, isobutylene trimer, 1, 2-butadiene, 1, 3-butadiene, 1, 2-pentadiene, 1, 3-pentadiene, 1, 4-pentadiene, isoprene, 1, 5-hexadiene, 2-methyl-5-propyl-1-hexene, 3-pentene, 4-octene and 3, 3-dimethyl-1 - pentene. In another embodiment, the olefin polymer is preparable by polymerization of a C ₄ refinery stream having a butene content of about 35 to about 75 weight percent and an isobutene content of about 30 to about 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes usually contain predominantly (greater than about 80% of the total repeating units) isobutene repeat units of the type (-CH 2 -C (CH 3) 2-)

In another embodiment, the polyalkene substituent of the polyalkene-substituted amine is derived from a polyisobutylene. In another embodiment, the amines that can be used to form the polyalkene-substituted amine include ammonia, monoamines, polyamines, or mixtures thereof, including mixtures of various monoamines, mixtures of various polyamines, and mixtures of monomines and polyamines (the diamines). , The amines include aliphatic, aromatic, heterocyclic and carbocyclic amines. Monoamines and polyamines are characterized by the presence in their structure of at least one HN <group. The amines can be aliphatic, cycloaliphatic, aromatic or heterocyclic. The monoamines are generally substituted by a hydrocarbon group of 1 to 50 carbon atoms. In particular, these hydrocarbon groups may be aliphatic and free of acetylenically unsaturated groups and may have 1 to about 30 carbon atoms. Particular mention may be made of saturated aliphatic hydrocarbon radicals having 1 to 30 carbon atoms.

In a further embodiment, the monoamines may have the formula HNR ₁ R ₂ wherein R 1 is a hydrocarbon group of up to 30 carbon atoms and R _{2 is} hydrogen or a hydrocarbyl group of up to about 30 carbon atoms. Examples of suitable monoamines are methylamine, ethylamine, diethylamine, 2-ethylhexylamine, di (2-ethylhexyl) amine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyl laurylamine and oleylamine.

Aromatic monoamines are those monoamines in which a carbon atom of the aromatic ring structure is bonded directly to the amine nitrogen atom. The aromatic ring will usually be a mononuclear aromatic ring (i.e., derived from benzene) but may have fused aromatic rings, and especially those derived from naphthalene. Examples of aromatic monoamines are aniline, di (para-methylphenyl) amine, naphthylamine, N- (n-butyl) aniline. Examples of aliphatic-substituted, cycloaliphatic-substituted and heterocyclic-substituted aromatic monoamines are: para-dodecylaniline, cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.

Hydroxyamines are also suitable monoamines. Such compounds are the hydroxyhydrocarbyl-substituted analogs of the aforementioned monoamines.

In one embodiment, the hydroxy monoamines are those of the formula HNR3R4, wherein R3 represents a hydroxy-substituted alkyl group of up to about 30 carbon atoms, and in one embodiment has up to about 10 carbon atoms; and R _{4 represents} a hydroxy-substituted alkyl group of up to about 30 carbon atoms, hydrogen or a hydrocarbyl group of up to about 10 carbon atoms. Examples of hydroxy-substituted monoamines include: ethanolamine, di-3-propanolamine, 4-hydroxybutylamine, diethanolamine and N-methyl-2-hydroxypropylamine.

In another embodiment, the amine of the polyalkene-substituted amines may be a polyamine. The polyamine may be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples of the polyamines include: alkylene polyamines, hydroxy group-containing polyamines, aryl polyamines and heterocyclic polyamines. The alkylene polyamines include those of the following formula

HN (R ⁵ ) - (alkylene-N (R ⁵ )) _n - (R ⁵ ) wherein n is in the range of 1 to about 10 and, for example, in the range of 2 to about 7, or 2 to about 5, and "Alkylene" group has 1 to about 10 carbon atoms, such as 2 to about 6, or 2 to about 4 carbon atoms;

each R ^{5 is} independently hydrogen, an aliphatic group, a hydroxyl or amine substituted aliphatic group of up to about 30 carbon atoms each. Typically, R ^{5 is} H or lower alkyl (an alkyl group of 1 to about 5 carbon atoms), especially H. Such alkylene polyamines include: methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines and heptylene polyamines. The higher homologs of such amines and related aminoalkyl substituted piperazines are also included.

Specific alkylenepolyamines for preparing the polyalkene-substituted amines are the following: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, 3-dimethylaminopropylamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, di (heptamethylene) triamine, tripropylenetetramine, pentaethylenehexamine , Di (trimethylene triamine), N- (2-aminoethyl) piperazine and 1,4-bis (2-aminoethyl) piperazine.

Ethylene polyamines, such as those mentioned above, are particularly suitable for reasons of cost and effectiveness. Such polyamines are described in detail in the chapter entitled "Diamines and Higher Amines" in Encyclopedia of Chemical Technology, Second Edition, Kirk-Othemer, Vol. 7, pp. 27-39, Interscience Publishers, Division of John Wiley & Sons, 1965. Such compounds are most conveniently prepared by reacting an alkylene chloride with ammonia or by reacting an ethyleneimine with a ring-opening reagent such as ammonia. These reactions lead to the preparation of complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines.

Other suitable types of polyamine mixtures are those formed by stripping the above-described polyamine mixtures as a residue and often referred to as "polyamine bottoms". In general, alkylene polyamine bottoms are those containing less than two, usually less than 1 wt% of material boiling below about 200 ° C. A typical example of such ethylene-polyamine bottoms are the "E-100" designated product. Dow Chemical Company of Freeport, Texas. These alkylenepolyamine bottoms include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetriamines, and the like. Hydroxyl-containing polyamines include: hydroxyalkylalkylenepolyamines having one or more hydroxyalkyl substituents on the nitrogen atoms. Such polyamines can be prepared by reacting the above-described alkylene polyamines with one or more alkylene oxides (e.g., ethylene oxide, propylene oxide, and butylene oxide). Similar alkylene oxide-alkanolamine reaction products can also be, for example, the products of the reaction of primary, secondary or tertiary alkanolamines with ethylene, propylene or higher epoxides in a molar ratio of 1: 1 to 1: 2. Reactant ratios and temperatures for carrying out such reactions are known to those skilled in the art.

In another embodiment, the hydroxyalkyl-substituted alkylene polyamine may be a compound in which the hydroxyalkyl group is a hydroxy-lower alkyl group, i. has less than eight carbon atoms. Examples of such hydroxyalkyl-substituted polyamines include N- (2-hydroxyethyl) ethylenediamine (also known as 2- (2-aminoethylamino) ethanol), N, N-bis (2-hydroxyethyl) ethylenediamine, 1- (2-hydroxyethyl) piperazine , monohydroxypropyl substituted diethylenetriamine, dihydroxypropyl-substituted tetraethylenepentamine and N- (3-hydroxybutyl) tetramethylenediamine.

Arylpolyamines are analogs to the above-mentioned aromatic monoamines. Examples of aryl polyamines include: N, N'-di-n-butyl-para-phenylenediamine and bis (para-aminophenyl) methane.

Heterocyclic mono- and polyamines may include: aziridines, azetidines, azolidines, pyridines, pyrroles, indoles, piperidines, imidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N , N'-diamino-alkylpiperazines, azepines, azocines, azonines, azecines and tetra-, di- and perhydro derivatives of each of the above compounds and mixtures of two or more of these heterocyclic amines. Typical heterocyclic amines are saturated 5- and 6-membered heterocyclic amines having only nitrogen, oxygen and / or sulfur in the heterocycle, especially piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines and the like. Piperidine, aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substituted piperazines, morpholine, aminoalkyl-substituted morpholines, pyrrolidine and aminoalkyl-substituted pyrrolidines are particularly preferred. Usually, the aminoalkyl substituents are attached to a nitrogen atom that is part of the heterocycle Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine and N, N'-diaminoethylpiperazine. Hydroxy-heterocyclic polyamines are also suitable, examples include: N- (2-hydroxyethyl) cyclohexylamine, 3-hydroxycyclopentylamine, parahydroxyaniline and N-hydroxyethylpiperazine.

Examples of polyalkene-substituted amines are the following: poly (propylene) amine, poly (butene) amine, N, N-dimethyl polyisobutylene amines; polybuteneemorpholines N-, N-poly (butene) -ethylenediamine, N-poly (propylene) trimethylenediamine, N-poly (butene), diethylenetriamine, N ', N'-poly (butene) tetraethylenepentamine and N, N-dimethyl-N' poly (propylene) -1,3-propylenediamine.

The number average molecular weight of such polyalkene-substituted amines is from about 500 to about 5,000, e.g. 1000 to about 1500 or about 500 to about 3000.

Any of the above polyalkene-substituted amines, which are secondary or primary amines, can be alkylated to tertiary amines with alkylating agents, also known as quaternizing agents, such as dialkyl sulfates, alkyl halides, hydrocarbyl-substituted carbonates; Hydrocarbylepoxiden in combination with an acid and mixtures thereof. When certain quaternizing agents such as alkyl halides or dialkyl sulfates are used, it may be necessary to provide a base or basic agent such as sodium carbonate or sodium hydroxide to give the free tertiary amine form. Primary amines require two equivalents of alkylating agent and two equivalents of base to obtain a tertiary amine. In another embodiment, the alkylation of primary amines can often be carried out in four consecutive steps, first a treatment with the alkylating agent followed by a second treatment with a base and then repeating the two steps. In another embodiment, the alkylation of a primary amine will occur in one step, for example, using two moles of alkyl halide in the presence of an excess of heterogeneous base, such as sodium carbonate. The polyamine can be exhaustively or partially alkylated in a manner known per se. In another embodiment, the alkylation of primary amines and secondary amines to tertiary amines can be done with epoxides. Unlike the alkyl halides, no base treatment is required when using an epoxide to obtain the free amine. Typically, alkylation of amines with epoxides will employ at least one mole of epoxide for each hydrogen atom on the amine. Alkylation to the tertiary amine with an epoxide requires neither additional acid nor base. Also particularly preferred is polyisobutene dimethylamine obtainable by hydroformylation of polyisobutene (Mn 1000) and subsequent reductive amination with dimethylamine, see Example B of WO 2008/060888. A3.4) reaction products of a hydrocarbyl-substituted acylating agent and a compound containing a nitrogen or oxygen atom and additionally containing at least one quaternizable amino group

Such compounds are e.g. described in the applicant's WO2013 / 000997, to which reference is expressly made.

The following may be mentioned as suitable hydrocarbyl-substituted polycarboxylic acid compounds or hydrocarbyl-substituted acylating agents: The polycarboxylic acid compounds used are aliphatic di- or polyvalent (such as 3- or 4-valent), in particular of di-, tri- or tetracarboxylic acids, and Analogs thereof, such as anhydrides or lower alkyl esters (partially or completely esterified), and optionally substituted by one or more (such as 2 or 3), in particular a long-chain alkyl radical and / or a high molecular weight hydrocarbyl radical, in particular a polyalkylene radical. Examples are C3-C10 polycarboxylic acids, such as the dicarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and their branched analogues; and the tricarboxylic acid citric acid; and anhydrides or lower alkyl esters thereof. The polycarboxylic acid compounds can also be produced from the corresponding monounsaturated acids and addition of at least one long-chain alkyl radical and / or high molecular weight hydrocarbyl radical. Examples of suitable monounsaturated acids are fumaric acid, maleic acid, itaconic acid.

The hydrophobic "long chain" or "high molecular weight" hydrocarbyl radical which provides sufficient solubility of the quaternized product in the fuel has a number average molecular weight (M ") of from 85 to 20,000, such as 1 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1, 500. Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and polyisobutenyl radicals, for example having a number average molecular weight M _n of 3,500 to 5,000, 350 to 3,000, 500 to 2,500, 700 to 2,500 and 800 to 1,500. Suitable hydrocarbyl-substituted compounds are described, for example, in DE 43 19 672 and WO2008 / 138836. Suitable hydrocarbyl-substituted polycarboxylic acid compounds also include polymeric, especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic acid compounds. Dimer forms contain, for example, two acid anhydride groups which can be reacted independently of one another in the inventive production process with the quaternizable nitrogen compound.

The quaternizable nitrogen compounds which are reactive with the above polycarboxylic acid compound are selected from a) hydroxyalkyl-substituted mono- or polyamines having at least one quaternised (eg choline) or quaternizable, primary, secondary or tertiary amino group, b) straight-chain or branched, cyclic, heterocyclic, aromatic or non-aromatic polyamines having at least one primary or secondary (anhydride-reactive) amino group and having at least one quaternized or quaternizable, primary, secondary or tertiary amino group;

c) piperazines.

In particular, the quaternizable nitrogen compounds are selected from

d) hydroxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines. e) straight-chain or branched aliphatic diamines having two primary amino groups;

Di- or polyamines having at least one primary and at least one secondary amino group; Di- or polyamines having at least one primary and at least one tertiary amino group; Di- or polyamines having at least one primary and at least one quaternary amino group; aromatic carbo-cyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group; Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those endowed with at least one, such as 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents.

As examples of "hydroxyalkyl-substituted monoamines" may be mentioned: N-hydroxyalkyl-monoamines, Ν, Ν-dihydroxyalkyl-monoamines and Ν, Ν, Ν-trihydroxyalkyl monoamines, wherein the hydroxyalkyl groups are the same or different and are also as defined above In this case, hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl. For example, the following "hydroxyalkyl-substituted polyamines" and in particular "hydroxyalkyl-substituted diamines" may be mentioned: (N-hydroxyalkyl) alkylenediamines, N, N-dihydroxyalkylalkylenediamines wherein the hydroxyalkyl groups are the same or different and also as defined above are. Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; Alkylene stands in particular for ethylene len, propylene or butylene.

Suitable "diamines" are alkylenediamines and the N-alkyl-substituted analogs thereof, such as N-monoalkylated alkylenediamines and the N, N or N, N'-dialkylated alkylenediamines. Alkylene is in particular straight-chain or branched C.sub.1-7 or C.sub.1-4. Alkylene, as defined above, is especially C 1 -C 4 -alkyl as defined above, examples being in particular ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and isomers thereof, pentanediamine and isomers thereof, Hexanediamine and isomers thereof, heptanediamine and isomers thereof, and mono- or polysubstituted, for example mono- or di-C 1 -C 4 -alkylated, for example methylated, derivatives of the abovementioned diamine compounds, such as 3-dimethylamino-1-propylamine (DMAPA), Ν, Ν-diethylaminopropylamine, and N, N-dimethylaminoethylamine.

Suitable straight-chain "polyamines" are, for example, dialkylenetriamine, trialkylenetetramine, tetraalkylenepentamine, pentaalkylenehexamine, and the N-alkyl-substituted analogs thereof, such as N-monoalkylated and the N, N or N, N'-dialkylated alkylene polyamines -7 or Ci-4-alkylene, as defined above.Alkyl is in particular Ci-4-alkyl as defined above.

Examples are in particular diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, pentabutylenehexamine; and the Ν, Ν-dialkyl derivatives thereof, in particular the N, N-di-Ci-4-alkyl derivatives thereof. Examples which may be mentioned are: Ν, Ν-dimethyldimethylenetriamine, N, N-diethyldimethylenetriamine, Ν, Ν-dipropyldimethylenetriamine, N, N-dimethyldiethylene-1,2-triamine, N, N-diethyldiethylene-1,2-triamine, N, N-dipropyldiethylene-1,2-triamine, N, N-dimethyl-dipropylene-1,3-triamine (ie DMAPAPA), N, N-diethyl-dipropylene-1,3-triamine, N, N-dipropyl-dipropylene-1,3-triamine, N, N-dimethyldibutylene-1,4-triamine, N, N-diethyldibutylene-1,4-triamine, N, N-dipropyldibutylene-1,4-triamine, N, N-dimethyldipentylene-1,5-triamine, N, N-diethyldipentylene-1,5-triamine, N, N-dipropyldipentylene-1,5-triamine, N, N-dimethyldihexylene-1,6-triamine, N, N-diethyldihexylene-1,6-triamine and N, N- Dipropyldihexylene-1,6-triamine, "Aromatic carbocyclic diamines" having two primary amino groups are the diamino substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthalene, fluorene, indene and phenanthrene. "Aromatic or non-aromatic heterocyclic polyamines" having two primary amino groups are the derivatives substituted with two amino groups of the following heterocycles:

5- or 6-membered saturated or monounsaturated heterocycles containing one to two nitrogen atoms and / or an oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members, eg. B. tetrahydrofuran, pyrrolidine, isoxazolidine, isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine, pyrroline, piperidine, piperidinyl, 1, 3-dioxane, tetrahydropyran, hexahydropyridazine, hexahydropyrimidine, piperazine;

5-membered aromatic heterocycles containing in addition to carbon atoms one, two or three nitrogen atoms or one or two nitrogen atoms and a sulfur or oxygen atom as ring members, for. Furan, thian, pyrrole, pyrazole, oxazole, thiazole, imidazole and 1, 3,4-triazole; Isoxazole, isothiazole, thiadiazole, oxadiazole

6-membered heterocycles containing in addition to carbon atoms one or two or one, two or three nitrogen atoms as ring members, for. Pyridinyl, pyridazine, pyrimidine, pyrazinyl,

1, 2,4-triazine, 1, 3,5-triazin-2-yl;

"Aromatic or non-aromatic heterocycles containing one primary and one tertiary amino group" are alkyl group carry Ci-4 ^", for example, the above-mentioned N-heterocycles which are aminoalkylated at least egg nem ring N atom, and especially an amino.

"Aromatic or non-aromatic heterocycles having a tertiary amino group and a hydroxyalkyl group" are, for example, the abovementioned N-heterocycles, which are hydroxyalkylated on at least one ring N atom, and in particular carry a hydroxy-C 1-4 -alkyl group.

The following groups of individual classes of quaternizable nitrogen compounds may be mentioned in particular:

Group 1 :

aromatics

Diaminobenzenes, e.g.

Diaminopyridines, e.g.

Group 2:

NAME FORMULA

heterocycles

1- (3-aminopropyl) imidazole

4- (3-aminopropyl) morpholine

1- (2-aminoethylpiperidine)

2- (1-piperazinyl) ethylamine (AEP) N

N-methylpiperazine N N-

Amines with tertiary second N atom

3,3-Diamino-N-methyldipropylamine

3-Dimethylamino-1-propylamine (DMAPA) I

N, N-diethylamino

2 \ ^ N

N, N-dimethylaminoethylamine I

Group 3:

2-dimethylamino-1-ethanol N

I

4-diethylamino-1-butanol

The reaction of the hydrocarbyl-substituted polycarboxylic acid compound with the quaternizable nitrogen compound can be carried out under thermally controlled conditions, so that substantially no condensation reaction takes place. In particular, no formation of reaction water is observed. In particular, such a reaction takes place at a temperature in the range of 10 to 80, in particular 20 to 60 or 30 to 50 ° C. The reaction time may be in the range of a few minutes or a few hours, e.g. about 1 minute to about 10 hours. The reaction can be carried out at about 0.1 to 2 atm pressure, but especially at about atmospheric pressure. For example, an inert gas atmosphere, such as e.g. Nitrogen, appropriate

In particular, the reaction can also be carried out under elevated, condensation-promoting temperatures, for. B. in the range of or 90 to 100 ° C or 100 to 170 ° C. The reaction time may be in the range of a few minutes or a few hours, e.g. about 1 minute to about 10 hours. The reaction can be carried out at about 0.1 to 2 atm pressure, but especially at about atmospheric pressure.

The reactants are presented in particular in approximately equimolar amounts, optionally a lower, z. 0.05 to 0.5 times, e.g. 0.1 to 0.3 times the molar excess of the polycarboxylic acid compound is desirable. If necessary, the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are e.g. Solvesso series solvent, toluene or xylene. The solvent can also serve, for example, azeotropically remove condensation water from the reaction mixture. In particular, however, the reactions are carried out without solvent.

The reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification. Particular mention may be made of the condensation product of polyisobutylene succinic anhydride (Glissopal® SA from BASF produced from polyisobutene (Mn 1000) and maleic anhydride in a known manner) and N, N-dimethyl-1,3-diaminopropane (CAS 109-55-7), see Production Example 1 of WO 2013/000997.

A4) Quaternizing agent:

In a further particular embodiment, the quaternization of the at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent selected from epoxides, in particular hydrocarbyl epoxides.

wherein the R _d radicals contained therein are the same or different and are H or a hydrocarbyl radical, wherein the hydrocarbyl radical has at least 1 to 10 carbon atoms. In particular, these are aliphatic or aromatic radicals, such as linear or branched C 1-10 -alkyl radicals or aromatic radicals, such as phenyl or C 1-4 -alkylphenyl.

Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic alkylene oxides, in particular C 2-12 -alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1, 2-pentenoxide, 2,3-pentenoxide, 2-methyl-1, 2-butene oxide, 3-methyl-1, 2-butene oxide, 1, 2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2-diene pentene; as well as aromatic-substituted ethylene oxides, such as optionally substituted styrene oxide, in particular styrene oxide or 4-methyl-styrene oxide.

In the case of using epoxides as quaternizing these are in the presence of free acids, especially in the presence of free hydrocarbyl-substituted unsaturated, especially saturated, optionally substituted, especially unsubstituted protic acids, such as especially with hydrocarbyl-substituted dicarboxylic acids, especially hydrocarbyl-substituted C3 -C28 or C3-Ci2 dicarboxylic acids, in particular unsubstituted, saturated C3-C6 dicarboxylic acid used ..

Suitable dicarboxylic acids are saturated acids, such as malonic, succinic, glutaric, adipic, pimelinic, suberic, azelaic, sebacic, undecanedioic and dodecanedioic acid, or hermolecular acids, such as tertiary, hexa- or octadecanedioic acid, such as malic acid, α-ketoglutaric acid, oxaloacetic acid; glutamic acid; aspartic acid; and unsaturated acids such as maleic acid and fumaric acid; such as in particular malonic, succinic, glutaric, adipic and pimelic acid.

Also suitable are aromatic dicarboxylic acid, e.g. Phthalic acid.

If required or desired, hydrocarbyl-substituted dicarboxylic acids can also be used in their anhydride form. For the quaternization, the ring opening of the anhydride is then effected by the addition of water.

Further embodiments of hydrocarbyl-substituted dicarboxylic acids:

The hydrocarbyl-substituted dicarboxylic acids can be prepared by hydrolysis of the corresponding hydrocarbyl-substituted dicarboxylic anhydrides in a manner known in principle, as described, for example, in DE 2443537. The hydrolysis is preferably carried out with stoichiometric amounts of water at temperatures of 50 to 150 ° C, but it can also be used an excess of water. The hydrolysis can be carried out without a solvent or in the presence of an inert solvent. Typical examples are e.g. Solvesso series solvents, toluene, xylene or straight and branched chain saturated hydrocarbons such as paraffins or naphthenes. The solvent may be removed after hydrolysis, but preferably remains and is used as a solvent or co-solvent for subsequent quaternization. Preferred hydrocarbyl-substituted dicarboxylic acid anhydrides are hydrocarbyl-substituted succinic anhydrides, such as those sold by the company Pentagon: n-dodecenylsuccinic anhydride CAS 19780-1 1 -1, n-Octadecenylbernsteinsäureanhydrid CAS. 28777-98-2, i-Octadecenyl succinic anhydride CAS. 28777-98-2, i-hexadecenyl succinic anhydride / i-octadecenyl succinic anhydride CAS 32072-96-1 & 28777-98-2, n-octenyl succinic anhydride CAS 26680-54-6. Tetrapropenyl succinic anhydride CAS. 26544-38-7.

Also preferred is polyisobutene succinic anhydride (PIBSA). The preparation of PIBSA from polyisobutene (PIB) and maleic anhydride (MSA) is known in principle and results in a mixture of PIBSA and bismaleinated PIBSA (BM PIBSA, see Scheme 1 below), which is generally not purified but further processed as such. The ratio of the two components to one another can be defined as the degree of bismaralization (BMG). ben. The BMG is known in principle (see US Pat. No. 5,883,196) and is determined as described in US Pat. No. 5,883,196.

Scheme 1

PIB MSA PIBSA BM PIBSA

Particularly preferred is PIBSA having a degree of bis-maleination up to 30, preferably up to 25 and more preferably up to 20%. As a rule, the degree of bismaleination is at least 2, preferably at least 5 and particularly preferably at least 10%. The targeted preparation is described for example in US 5,883,196. In particular, highly reactive PIB (HR-PIB) with Mn in the range from 500 to 3000, for example 550 to 2500, 800 to 1200 or 900 to 1100, is suitable for the preparation. Mn is determined by GPC as described in US 5,883,196. Particularly preferred PIBSA prepared from HR-PIB (Mn = 1000) has saponification numbers of 85-95 mg KOH / g.

A non-limiting example of a particularly suitable PIBSA is Glissopal SA ^® F from. BASF prepared from HR-PIB (Mn = 1000) with a Bismaleinierungsgrad of 15% and a saponification number of 90 mg KOH / g.

It is also conceivable, although less preferred, to react the abovementioned hydrocarbyl-substituted dicarboxylic acid anhydrides instead of water with an alcohol, preferably a monoalcohol, particularly preferably an alkanol or an amine, to give the corresponding monoester or monoamide of the hydrocarbyl-substituted dicarboxylic acids , It is important that in such a reaction, an acid function remains in the molecule.

If the quaternization is carried out in the presence of an alcohol, the same alcohol is preferably used for such a reaction of the hydrocarbyl-substituted dicarboxylic anhydrides, such as 2-ethylhexanol or 2-propylheptanol as solvent in the quaternization, and also butyldiglycol, butylglycol, methoxypropoxypropanol or Butoxy dipropanol. Such alcoholysis is preferably carried out with stoichiometric amounts of alcohol or amine at temperatures of 50 to 150 ° C, but it can also be an excess of alcohol or amine, preferably alcohol are used. This then expediently remains in the reaction mixture and serves as a solvent in the subsequent quaternization.

A5) Preparation of Inventive Additives: a) Quaternization The quaternization with an epoxide of the formula (4) is carried out in principle on the basis of known processes. If the boiling point of a component of the reaction mixture, in particular of the epoxide, at normal pressure above the reaction temperature, the reaction is conveniently carried out in an autoclave. For example, in an autoclave, a solution of the tertiary amine with the organic hydrocarbyl substituted dicarboxylic acid (such as polyisobutene-succinic acid) is added in the required approximately stoichiometric amounts. For example, 0.1 to 2.0, 0.2 to 1.5, or 0.5 to 1.25 equivalents of dicarboxylic acid can be used per equivalent of quaternizable tertiary nitrogen atom. In particular, however, approximately approximately molar proportions of dicarboxylic acid are used. The mixture is then sufficiently purged with N ₂ , and adjusted to a suitable form and the epoxide (eg propylene oxide) is metered in the required stoichiometric amounts at a temperature between 20 ° C and 180 ° C. For example, 0.1 to 4.0, 0.2 to 3, or 0.5 to 2 equivalents of epoxide can be used per equivalent of quaternizable tertiary nitrogen atom. In particular, however, about 1 to 2 equivalents of epoxide are used in relation to the tertiary amine in order to completely quaternize the tertiary amine group. In particular, a molar excess of alkylene oxide can be used, whereby the free carboxyl group of the dicarboxylic acid is partially or completely esterified. The mixture is then cooled for a suitably long period of time from a few minutes to about 24 hours, for example for about 10 hours at a temperature between 20 ° C. and 180 ° C. (eg 50 ° C.), for example to about 20 to 50 ° C, rinsed with N2 and the reactor emptied.

The reaction can be at about 0.1 to 20 bar, such as. 1 to 10 or 1, 5 to 5 bar pressure. The reaction can also be carried out at atmospheric pressure. In particular, an inert gas atmosphere, such as e.g. Nitrogen, appropriate.

If necessary, the reactants may be in a suitable inert organic aliphatic or aromatic solvent or mixture thereof, for quaternization be submitted. Typical examples are, for example Solvesso series solvents, toluene or xylene or 2-ethylhexanol, or 2-propylheptanol, and also butyldiglycol, butylglycol, methoxypropoxpropanol, butoxydipropanol or straight-chain and branched saturated hydrocarbons, such as paraffins or naphthenes. However, the quaternization can also be carried out in the absence of a solvent.

The quaternization may be carried out in the presence of a protic solvent, optionally also in combination with an aliphatic or aromatic solvent. In particular, suitable protic solvents have a dielectric constant (at 20 ° C.) of greater than 7. The protic solvent may contain one or more OH groups and may also be water. Suitable solvents may also be alcohols, glycols and glycol ether. In particular, suitable protic solvents may be those mentioned in WO 2010132259. Particularly suitable solvents are methanol, ethanol, n-propanol, isopropanol, all isomers of butanol, all isomers of pentanol, all isomers of hexanol, 2-ethylhexanol, 2-propylheptanol, as well as mixtures of various alcohols. The presence of a protic solvent can positively influence the conversion and reaction rate of quaternization. b) work-up of the reaction mixture

The final reaction product thus formed can theoretically be further purified or the solvent removed. Optionally, excess reagent, such as excess epoxide, may be removed. This can be done for example by introducing nitrogen at atmospheric pressure or under reduced pressure. In order to improve the further processability of the products, however, it is also possible to add solvents after the reaction, e.g. Solvesso series solvent, 2-ethylhexanol, or substantially aliphatic solvents. Usually, however, this is not absolutely necessary, so that the reaction product can be used without further purification as an additive, if appropriate after mixing with further additive components (see below).

It is a preferred embodiment of the present invention that the quaternized ammonium compounds have a weight loss in a thermogravimetric analysis (TGA) at 350 ° C of less than 50 wt .-%, such as less than 40, less than 35, less than 30, less than 20 or less than 15, such as up to 0 to 5 wt .-% have weight loss. For this purpose, a thermogravimetric analysis (TGA) according to the standard ISO-4154 is performed. Specifically, in the test, a run is made from 50 ° to 900 ° C at a temperature rise rate of 20 ° C per minute under a nitrogen atmosphere at a flow rate of 60 mL per minute.

use

The use according to the invention relates to the inhibition of the corrosion of iron, steel and / or non-ferrous metal surfaces.

Of the non-ferrous metals, copper and its alloys are preferred.

Particularly preferably, the corrosion of steel surfaces is inhibited. The reaction products described are fuels having the above-specified content of alkali and / or alkaline earth metals and / or zinc for the action as a corrosion inhibitor, usually in amounts of 1 to 60, preferably 4 to 50 wt. Ppm and particularly preferably 10 to 40 Ppm by weight added. In order to show an effect against deposits on valves and / or antistatic effect, the reaction products described are generally added to the fuels in amounts of from 10 to 120, preferably from 20 to 100, ppm by weight and more preferably from 30 to 80 ppm by weight. Frequently, the reaction products described are used in the form of fuel additive mixtures, together with customary additives:

In the case of diesel fuels, these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the described reaction products, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents , Metallocenes, metal deactivators, dyes and / or solvents.

In the case of gasoline fuels, these are mainly friction modifiers, corrosion inhibitors other than the described reaction products, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.

Typical examples of suitable co-additives are listed in the following section:

B1) Detergent additives Preferably, at the usual detergent additives are amphiphilic substances which have at least one hydrophobic hydrocarbon radical having a number average molecular weight (M _n) from 85 to 20,000 and having at least one polar moiety which is selected from:

(Da) mono- or polyamino groups having up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties;

(Db) nitro groups, optionally in combination with hydroxyl groups;

(De) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;

(Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;

(De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;

(Df) polyoxy-C 2 to C 4 -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;

(Dg) carboxylic acid ester groups;

(Ie) derived from succinic anhydride moieties having hydroxy and / or amino and / or amido and / or imido groups; and or

(Di) by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings.

The hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel has a number average molecular weight (M _n ) of from 85 to 20,000, preferably from 1 13 to 10,000, more preferably from 300 to 5,000, more preferably from 300 up to 3,000, more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1,500. The typical hydrophobic hydrocarbon radicals are in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M _n of preferably from 300 to 5,000, particularly preferably from 300 to 3,000, more preferably from 500 to 2,500, even more preferably from 700 to 2,500 and in particular from 800 to 1,500. As examples of the above groups of detergent additives, the following are mentioned:

Mono- or polyamino (Da) -containing additives are preferably polyalkene mono- or polyalkene polyamines based on polypropene or of highly reactive (ie with predominantly polybutene or polyisobutene having M _n = 300 to 5,000, particularly preferably 500 to 2,500 and in particular 700 to 2,500. Such additives based on highly reactive polyisobutene, which consist of the polyisobutene, the bis can contain up to 20 wt .-% of n-butene units, can be prepared by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethyl-aminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine are, in particular from EP -A 244 616 known. If one starts with the preparation of the additives of polybutene or polyisobutene with predominantly intermediate double bonds (usually in the β and γ position), the preparation route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. For amination here amines, such as. As ammonia, monoamines or the above polyamines, are used. Corresponding additives based on polypropene are described in particular in WO-A 94/24231.

Other particular monoamino (Da) containing additives are the hydrogenation of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946.

Further special monoamino (Da) -containing additives are the compounds obtained from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.

Nitro groups (Db), optionally in combination with hydroxyl groups, containing additives are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A96 / 03367 and in WO-A 96/03479 are described. As a rule, these reaction products are mixtures of pure nitropolyisobutenes (for example α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example α-nitro-β-hydroxy polyisobutene). Hydroxyl groups in combination with mono- or polyamino groups (De) containing additives are in particular reaction products of polyisobutene epoxides, obtainable from preferably predominantly terminal double bonds having polyisobutene with M _n = 300 to 5000 with ammonia, mono- or polyamines, as described in particular in EP-A 476 485.

Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C ₂ - to C4o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partly to the alkali metal. metal or alkaline earth metal salts and a remaining radical of the carboxyl groups are reacted with alcohols or amines. Such additives are known in particular from EP-A 307 815. Such additives are mainly used to prevent valve seat wear and, as described in WO-A 87/01 126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) -butene amines or polyetheramines.

Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobern- steinsäurealkylesters, as described in particular in EP-A 639 632. Such additives are mainly used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.

Polyoxy-C2-C4-alkylene (Df) containing additives are preferably polyether or polyetheramines, which by reaction of C2 to C6o-alkanols, C6 to C30 alkanediols, mono- or D1-C2 to C3o-alkylamines, C1- to C3o-alkylcyclo-hexanols or C1- to C3o-alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available , Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. In the case of polyethers, such products also fulfill carrier oil properties. Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and the corresponding reaction products with ammonia.

Carboxyl ester groups (Dg) -containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm ² / s at 100 ° C, as described in particular in DE-A 38 38 918 are described. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties. Derivatives derived from succinic anhydride with hydroxyl and / or amino and / or amido and / or imido (Dh) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenyl succinic anhydride, which by reaction of conventional or highly reactive polyisobutene having M _n = preferably 300 to 5000, more preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by thermal means in an ene reaction or via the chlorinated polyisobutene are available. The moieties having hydroxy and / or amino and / or amido and / or imido groups they are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboximides with diamines or polyamines, in addition to the imide function still have free amine groups, or diimides formed by the reaction of di- or polyamines with two succinic acid derivatives. Such fuel additives are well known and described, for example, in documents (1) and (2). Preference is given to the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines, and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest here are reaction products with aliphatic polyamines (polyalkyleneimines), in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.

Mannich-containing additives produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine , The polyisobutenyl-substituted phenols may be derived from conventional or highly reactive polyisobutene having M _n = 300 to 5,000. Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.

One or more of said detergent additives may be added to the fuel in such an amount that the metering rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm.

B2) carrier oils

Co-used carrier oils may be mineral or synthetic. Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils having viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil" known and obtained in the refining of mineral oil fraction (Vakuumdestillatschnitt with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.

Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyternal olefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols. Examples of suitable polyolefins are olefin polymers having M _n = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C ₂ - to C ₄ -alkylene groups which are prepared by reacting C ₂ - to C 60 -alkanols, C ₆ - to C ₃ -alkanediols, mono- or C 1 - to C 20 -alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, Monoamines or polyamines are available. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, as polyetheramines, poly-C 2 to C 6 alkylene oxide amines or functional derivatives thereof can be used. Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.

Examples of carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B. di- (n- or isotridecyl) phthalate. Further suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C3 to C6 alkylene oxide units, for. For example, propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is, in particular, a straight-chain or branched C 6 - to C 18 -alkyl radical. Specific examples include tridecanol and nonylphenol. Particularly preferred alcohol-initiated polyethers are the reaction products (polyetherification products) of monohydric C6- to Cis-aliphatic alcohols with C3- to C6-alkylene oxides. Examples of monohydric aliphatic C6-Cis alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and position isomers. The alcohols can be used both in the form of pure isomers and in the form of technical mixtures. A particularly preferred alcohol is tridecanol. Examples of C3 to C6 alkylene oxides are propylene oxide, such as 1, 2-propylene oxide, butylene oxide, such as 1, 2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Among these, particular preference is given to C ₃ -C ₄ -alkylene oxides, ie propylene oxide, such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Specifically, butylene oxide is used.

Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.

Particular carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred. The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight.

B3) cold flow improver

Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility. In particular, the usually used for middle distillates of fossil origin, ie for conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI") come into consideration. However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFI and / or which act as WASA and / or as nucleators.

Typically, the cold flow improver is selected from:

(K1) copolymers of a C2- to C4o-olefin with at least one further ethylenically unsaturated monomer;

(K2) comb polymers;

(K3) polyoxyalkylenes;

(K4) polar nitrogen compounds;

(K5) sulfocarboxylic acids or sulfonic acids or their derivatives; and

(K6) poly (meth) acrylic acid esters.

Mixtures of different representatives from one of the respective classes (K1) to (K6) as well as mixtures of representatives from different classes (K1) to (K6) can be used.

Suitable C 2 - to C 4 -olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular a carbon-carbon double pelbindung. In the last In this case, the carbon-carbon double bond can be arranged both terminally (α-olefins) and internally. However, preference is given to α-olefins, particularly preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, ethylene.

In the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins. If further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 - to C 4 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, suitable further olefins are, in particular, C 10 - to C 40 -alpha-olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.

Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 2 to C 20 alkanols, in particular C 1 to C 10 alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol, and structural isomers thereof.

Suitable carboxylic alkenyl esters are, for example, C2 to C-u-alkenyl esters, e.g. the vinyl and propenyl esters of carboxylic acids having from 2 to 21 carbon atoms, the hydrocarbon radical of which may be linear or branched. Preferred among these are the vinyl esters. Among the carboxylic acids having a branched hydrocarbon radical, preference is given to those whose branching is in the α-position relative to the carboxyl group, the α-carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear.

Examples of suitable carboxylic alkenyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred. A particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA").

Particularly advantageous ethylene-vinyl acetate copolymers and their preparation are described in WO 99/29748.

Suitable copolymers of class (K1) are also those which contain two or more mutually different carboxylic acid alkenyl esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form. Also terpolymers of a C ₂ - to C4o-α-olefin, a C ₁ - to C 20 -alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C ₂ - to C ₄ - alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are suitable as copolymers of class (K1). Such terpolymers are described in WO 2005/054314. A typical such terpolymer is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.

The at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight. %, based on the total copolymer, copolymerized. The majority by weight of the monomer units in the copolymers of class (K1) thus usually comes from the C2 to C ₄ o-based olefins.

The copolymers of class (K1) preferably have a number average molecular weight M _{n of} from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.

Typical comb polymers of component (K2) are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol available with at least 10 carbon atoms. Other suitable comb polymers are copolymers of olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers may also be polyfumarates or polymaleinates. In addition, homopolymers and copolymers of vinyl ethers are suitable comb polymers. Comb polymers suitable as component of class (K2) are, for example, those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", N.A. Plate and V.P. Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 1 17 to 253 (1974). "Mixtures of comb polymers are also suitable.

Polyoxyalkylenes suitable as a component of class (K3) are, for example, polyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two, linear alkyl groups each having from 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5,000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US Pat. No. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. Further, polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms such as stearic acid or behenic acid are suitable. Polar nitrogen compounds suitable as a component of class (K4) may be of both ionic and nonionic nature, and preferably have at least one, especially at least two, tertiary nitrogen substituent of the general formula> NR ⁷ , wherein R ^{7 is} Cs to C 40 Hydrocarbon residue stands. The nitrogen substituents may also be quaternized, ie in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. Preferably, the amines contain at least one linear Cs to C4o-alkyl radical. Examples of suitable primary amines for preparing said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues, secondary amines which are suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine. Also suitable for this purpose are amine mixtures, in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic". Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.

In particular, the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines. The poly (C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5, carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units. The carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.

The component of the class (K4) is preferably an oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) having the general formula IIa or IIb and having at least one tertiary amino group

HOOC_ _D .COOH

B B

i i

HOOC ._. L \ k _A Vk _D .COOH

BAB (IIa)

(IIb) in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III

HOOC '^ N' ⁰ "^2'0" ^{2 '}

1

CH ₂ -CH ₂ - and the variable B denotes a C to Cig-alkylene group. The compounds of the general formula IIa and IIb have in particular the properties of a WASA.

Furthermore, the preferred oil-soluble reaction product of component (K4), in particular that of general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.

Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1, 1-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene, 1, 4-butylene ethylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexa-1-propylene), methylene) and in particular 1, 2-ethylene. Preferably, the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms. Cr to Ci ₉ -Alkylengruppen the variable B are, for example, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, Tetradecamethyl- en, hexadecamethylene, octadecamethylene, nonadecamethylene and especially methylene , Preferably, the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms. The primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines may be selected from a variety of amines bearing hydrocarbon radicals, optionally linked together. Most of these amines which are the oil-soluble reaction products of component (K4) are secondary amines and have the general formula HN (R ⁸ ) 2 in which the two variables R ⁸ independently of one another each represent straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C24-alkyl radicals mean. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the abovementioned secondary amines are derived, with regard to their longer-chain alkyl radicals, from naturally occurring fatty acids or from their derivatives. Preferably, the two radicals R ^{8 are the} same.

The abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, there are few or none free acid groups. Preferably, the oil-soluble reaction products of component (K4) are completely in the form of the amide structures.

Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or especially ditallow fatty amine. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.

Further typical examples of component (K4) are the N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates, for example the reaction product of 1 mol of phthalic anhydride and 2 mol of ditallow fatty amine, the latter hydrogenated or unhydrogenated and the reaction product of 1 mole of an alkenyl spiro-bis-lactone with 2 moles of a dialkylamine, for example, ditallow fatty amine and / or tallow fatty amine, the latter two of which may be hydrogenated or unhydrogenated.

Further typical structural types for the component of the class (K4) are cyclic compounds having tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/181 15.

Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic acid esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957 to be discribed.

As a cold flow improver of the component of the class (K6) suitable poly (meth) acrylic acid esters are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight-average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C14 and Cis alcohols, wherein the acid groups are neutralized with hydrogenated talla- min. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.

The middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 50 to 1000 ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight. B4) Lubricity improver

Suitable lubricity improvers (or friction modifiers) are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described for example in WO 98/004656, and glycerol monooleate. The reaction products of natural or synthetic oils, for example triglycerides, and alkanolamines described in US Pat. No. 6,743,266 B2 are also suitable as such lubricity improvers. B5) Other corrosion inhibitors than the described reaction product

Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany), Irgora® L12 (BASF SE) or HiTEC 536 (Ethyl Corporation).

B6) Demulsifiers

Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalenesulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenolethoxylate or tert-pentylphenolethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.

B7) Dehazer

Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) products available under the tradename.

B8) antifoam

Suitable antifoams are e.g. Polyether-modified polysiloxanes such as the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.

B9) Cetane number improvers Suitable cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.

B10) Antioxidants Suitable antioxidants are, for example, substituted phenols, such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol, and also phenylenediamines, such as N, N'-di-sec-butyl-p-phenylenediamine.

B1 1) Metal deactivators

Suitable metal deactivators are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.

B12) Solvent

Suitable ones are e.g. nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, xylenes, white spirit, and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents, for example, alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually arrive together with the aforementioned additives and co-additives which they are intended to dissolve or dilute for better handling into the diesel fuel.

C) fuels

The use according to the invention relates in principle to any fuels, preferably diesel and gasoline fuels.

Middle distillate fuels, such as diesel fuels or fuel oils, are preferably petroleum raffinates, which usually have a boiling range of from 100 to 400.degree. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called "Ultra Low Sulfur Diesel" or "City Diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of for example, 285 ° C and a sulfur content of not more than 0.001 wt .-%. In addition to the mineral middle distillate fuels or diesel fuels obtainable by refining, those which are obtained by coal gasification or gas liquefaction [GTL] or by biomass liquefaction [BTL], Fuels] are available, suitable. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.

The qualities of fuel oils and diesel fuels are specified in greater detail in, for example, DIN 51603 and EN 590 (cf., also, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A12, page 617 et seq.).

The use according to the invention in middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, also relates to mixtures of such middle distillates with biofuel oils (biodiesel). Such The term "middle distillate fuel" encompasses the term "middle distillate fuel". They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel.

Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats. Alkyl esters are usually lower alkyl esters, especially C 1 to C ₄ alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, for example ethanol or especially methanol ("FAME ") are available. Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biofuel oil or components thereof are, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME") and in particular rapeseed oil methyl ester ( "RME").

The middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less as 0.005 wt .-% and especially less than 0.001 wt .-% sulfur.

As gasoline fuels are all commercially available gasoline fuel compositions into consideration. A typical representative here is the market-standard basic fuel of Eurosuper according to EN 228. Furthermore, gasoline compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention.

The following examples are intended to illustrate the present invention without limiting it. Examples

GPC analysis

Unless otherwise stated, the weight average Mw and number average molecular weight Mn of the polymers were measured by gel permeation chromatography (GPC). GPC separation was achieved via two PLge Mixed B columns (Agilent) in tetrahydrofuran at 35 ° C. The calibration was carried out by means of a narrowly distributed polystyrene standard (PSS, Germany) with molecular weight 162-50400 Da. Hexylbenzene was used as a low molecular weight marker. Preparation Examples

Preparation Examples 1 to 4: Quaternization of tertiary fatty amines with propylene oxide in the presence of various hydrocarbyl-substituted succinic acids

Ri stands for long-chain hydrocarbyl; R _2, R ₃ and R ₄ correspond to R _a , R b and R _c are as defined above; R ₅ corresponds to R _d as defined above; and R is H or is a residue produced by esterification with the epoxide such as -CH 2 CH (Rs) OH

a) Reagents used: polyisobutylenesuccinic anhydride (PIBSA, Glissopal® SA, BASF):

Made from maleic anhydride and polyisobutene 1000 in known manner. Unless otherwise stated, grades having a degree of bismaleination of 10 to 20% and saponification numbers in the range of 84-95 mg KOH / g were used for the preparation examples according to the invention. To prepare polyisobutylenesuccinic acid, polyisobutylenesuccinic anhydride was mixed with an equimolar amount of water in accordance with the saponification number and hydrolyzed at a temperature of 80.degree. For example, the reaction of polyisobutylene succinic anhydride (saponification number 85.6 mg KOH / g) after 4 h reaction time at 80 ° C gave a reaction product having an acid number of 83.9 mg KOH / g. The formation of polyisobutylenesuccinic acid was confirmed by IR spectroscopy (171 1 cm ^-1 ). In an analogous manner, tetrapropenylsuccinic anhydride (CAS 26544-38-7) and a mixed i-hexadecenyl / i-octadecenylsuccinic anhydride (CAS 32072-96-1 and 28777- 98-2) from Pentagon were hydrolyzed to the corresponding succinic acid derivatives. Cocoyldimethylamine: (N, N-dimethyl-N-C12 / 14-amine, CAS 68439-70-3 or 1 12-18-5) with a total amine number of 246 mg KOH / g.

N-methyl-N, N-ditallow fatty amine: Armeen® M2HT from Akzo Nobel, CAS 61788-63-4, with a total amine number of 108 mg KOH / g. Next was used:

Ν, Ν-dimethylhexadecylamine (n-Ci ₆ H ₃ 3NMe 2, CAS 1 12-69-6, Aldrich).

Tridecylamine (branched, isomer mixture, CAS 86089-17-0) from BASF.

N, N-dimethyl-1,3-diaminopropane (DMAPA, CAS 109-55-7) from BASF.

2-ethylhexanol and 2-propylheptanol from BASF.

Solvent naphthalene depleted (ND): Solvesso ™ 150 ND from Exxon Mobil. b) General Synthesis Instructions

In a 2 l autoclave, a solution of the tert. Amine (1 eq. According to the total amine number) and the Alkylenbernsteinsäurederivats (1 eq. According to the acid number) in the specified solvent (2-ethylhexanol, unless otherwise stated) submitted. The amount of solvent and the batch size are chosen such that the end product has an active content of 50% and the reactor has a fill level of about 70%. Then it is rinsed three times with N2, a pre-pressure of approx. 2 bar N2 is set and the temperature is increased to 50.degree. The specified alkylene oxide, unless stated otherwise Propylene oxide (2 eq.) Is added within 1 h. The mixture is then stirred for 15 h at 50 ° C, cooled to 25 ° C, rinsed with N2 and the reactor emptied. The product is transferred to a 2 L jacketed reactor and excess alkylene oxide is removed by passing an IS stream (10 l / h) under vacuum (70 mbar) at 50 ° C for 6 h. ¹ H-NMR (CDC) confirms the quaternization (δ = 3.3 ppm, singlet, R ₂ N (CH ₃ ) 2 and R3NCH3, respectively).

c) Experiments performed

Following the above procedure, the following quaternizations were carried out with propylene oxide: Production tert. Amine hydrocarbyl-substituted

for example succinic acid

1 cocoyldimethylamine polyisobutylenesuccinic acid

2 cocoyldimethylamine tetrapropenylsuccinic acid

3 Cocoyldimethylamine i-hexadecenyl / i-octadecenyl succinic acid

4 N-Methyl-N, N-Ditalgfettamine Tetrapropenylsuccinic acid

6 n-Ci ₆ H ₃ 3NMe2 polyisobutylenesuccinic acid

7 n-Ci ₆ H33NMe ₂ polyisobutylenesuccinic acid

8 n-Ci ₆ H33NMe ₂ polyisobutylenesuccinic acid

9 n-Ci ₆ H33NMe ₂ polyisobutylenesuccinic acid

10 n-Ci ₆ H33NMe ₂ polyisobutylenesuccinic acid

1 1 n-Ci ₆ H ₃ 3NMe ₂ polyisobutylenesuccinic acid

12 n-Ci ₆ H ₃₃ NMe ₂ polyisobutylenesuccinic acid

13 Cocoyldimethylamine Polyisobutylenesuccinic acid

16 N, N-dimethylethanolamine * 15 PO tetrapropenyl succinic acid

17 PI BSA-DMAPA Succinimide Tetrapropenyl succinic acid

Notes on production example:

No. 7: 2-Propylheptanol was used instead of 2-ethylhexanol as a solvent.

No. 8: 2-Ethylhexanol / Solvent Naphtha ND 1: 1 (w / w) was used in place of 2-ethylhexanol

Solvent used.

# 9: Ethylene oxide (1.5 eq.) Instead of propylene oxide was used. 2-Propylheptanol was used as the solvent instead of 2-ethylhexanol.

# 10: The PI BSA used (from maleic anhydride and polyisobutene 1000) had one

Bismaleinierungsgrad of 32% and a saponification number of 1 12.5 mg KOH / g. No. 1 1: 1, 5 eq. Propylene oxide was used.

No. 12: 1, 1 eq. Propylene oxide was used.

No. 13: 2-Propylheptanol was used instead of 2-ethylhexanol as a solvent. The PI BSA used (from maleic anhydride and polyisobutene 550) had a saponification number of 142.5 mg KOH / g.

No. 16: 2-propylheptanol was used as solvent, the amine obtained was a polyetheramine obtained by 15-fold propoxylation of Ν, Ν-dimethylethanolamine (preparation see Synthesis Example 1 of WO 2013/064689 A1). No. 17: 2-Propylheptanol was used as a solvent, as the amine, the condensation product of polyisobutylenesuccinic acid (PIBSA) and DMAPA was used, see Preparation Example 1 of WO 2013/000997 A1. Production Example 5: Quaternization of trimethylamine with dodecenecoxide in the presence of tetrapropenylsuccinic acids

Reagents: Dodecene oxide (CAS 2855-19-8) from Aldrich, trimethylamine (anhydrous, CAS 75-50-3) from BASF

In a 2 l autoclave rendered inert with N 2, a solution of trimethylamine (47.2 g, 0.8 mol) and dodecene oxide (147.2 g, 0.8 mol) in 2-ethylhexanol (194.4 g) is introduced. Then the temperature is raised to 40 ° C. A solution of tetrapropenylsuccinic acid (252.8 g, 0.8 mol) in 2-ethylhexanol (252.8 g) is added over 1.5 h. The mixture is then stirred at 40 ° C for 15 h. Volatile components are removed by introducing an IS stream at 40 ° C, then the reactor is emptied. ¹ H NMR (CDCl 3) confirms quaternization (δ = 3.3 ppm, singlet, RN (CH ₃ ) ₃ ).

Preparation Example 14: Synthesis of iCi3NMe2

Tridecylamine (140.2 g) is introduced at room temperature and admixed with stirring within 15 min with formic acid (166.7 g). The reaction mixture is heated to 45 ° C and aqueous formaldehyde solution (37%, 132.7 g) is added dropwise with evolution of CO 2 within 25 min. The mixture is then stirred at 80 ° C for 23 h. After cooling to room temperature, hydrochloric acid (32%, 121.5 g) is added with stirring. The mixture is stirred for 3 h at room temperature and the water removed on a rotary evaporator in vacuo. The product mixture is mixed with 500 ml of water and with 50% sodium hydroxide solution, the amine is released. It was extracted twice with methyl tert-butyl ether, the combined organic phases were dried over sodium sulfate and the solvent was removed on a rotary evaporator. The product (143.5 g) showed a total amine number of 228 mg KOH / g with 94% tert. Amine.

Preparation 15: Quaternization of iCi3NMe2 with propylene oxide / tetrapropenyl succinic acid

According to the general procedure, iCi3NMe2 (Preparation 14), tetrapropenylsuccinic acid and propylene oxide were reacted in 2-propylheptanol instead of 2-ethylhexanol. Analytical Example 1 a) Determination of Quaternization Level

Quaternization levels are determined by ¹ H NMR spectroscopy. For this purpose, the corresponding solvent is removed with a Kugelrohr still (60 ° C., p = 10 ^-3 mbar, 3 h) To determine the degree of quaternization, the alkyl portion is integrated with the signals of the quaternized product RCH 2 NMe CH 2 CH (OH) R ^' The integral values of the signals of the quaternized product and the corresponding theoretical values multiplied by 100% give the degree of quaternization and the values for the various signals are averaged, solvent residues (doublet at δ = 3.55 ppm for HOCH2CHRR ^' ) are taken into account.

b) Thermogravimetry

For thermogravimetric analysis, the corresponding solvent was removed with a Kugelrohr still (60-70 ° C., p = 10 ^-3 mbar, 3 h) .The thermogravimetry was measured from 30 ° C. to 900 ° C. with a temperature increase of 20 ° C. under nitrogen atmosphere at a flow rate of 60mL / min The following mass changes (TG) at 350 ° C were determined:

applications

From the above synthesis examples, by mixing with polyisobuteneamine (molar mass 1000), polypropylene glycol as carrier oil and solvent and dehazer, the given additive formulations and used in the application examples (compositions in parts by weight).

A) Calcium Tolerance Test:

100 ml motor oil (Shell Helix®, with a Ca content of 1500 ppm, Mg content 1 100 ppm and Zn content 1300 ppm) were heated to 70 ° C. in a beaker and then 1 ml of corrosion inhibitor was added. If the solution is still clear, add another 1 ml of inhibitor. If the solution becomes cloudy, the test is considered failed (e.g., Figure 1, left beaker).

Figure 1 shows the with 1 mL of product according to Synthesis Example 7 (50% in 2-propylheptanol) offset, clear oil right. In the left beaker, 1 mL dimer fatty acid (dimeric acid, CAS: 61788-89-4, 40% in solvent naphtha) was used as a comparison. One recognizes a clearly visible turbidity.

B) Conductivity test:

A conductivity measurement according to DIN 51412 was carried out: Haltermann E0 base fuel: 58 ps / m

Formulation 1 (vs) (894 mg / kg additive): 70 ps / m

Formulation 2 (894 mg / kg additive): 83 ps / m

It can be seen that the conductivity can be significantly increased by the compound according to the invention from manufacturing example 7.

C) Steel finger corrosion according to ASTM D 665B: a) Otto fuel

The fuel used was commercial petrol 95 octane E0 from Haltermann and added to Table 1 and subjected to a corrosion test in accordance with ASTM D 665 B.

As a comparison, dimer fatty acid (dimeric acid, CAS: 61788-89-4 as a corrosion inhibitor dissolved in solvent naphtha) was used in formulation 3. Additive Dosage NACE Rating

Haltermann EO GrundkraftE

material

Formulation 3 (cf.) 500 mg / kg A

Formulation 4 500 mg / kg A

Formulation 5 490 mg / kg E

The evaluation was as follows: A 100% stainless

B ++ 0.1% or less of the entire surface rusted

B + 0.1% to 5% of the total surface rusted

B 5% to 25% of the entire surface rusted

C 25% to 50% of the entire surface rusted

D 50% to 75% of the total surface rusted

E 75% to 100% of the total surface rusted b) Diesel fuel Commercially available diesel fuel Aral DIN 590 was used as the fuel and tested with artificial seawater in accordance with DIN D665B (modified).

In Figure 2, left, the specimen is shown, which was tested in the fuel without further additives (NACE "E" rating).

In Figure 2, right, the specimen is shown, which was tested in the fuel with the addition of 32 mg / kg of Preparation Example 7 (based on active substance) (NACE "A" rating). D) PFI motor test DC M1 1 1 E

An engine test was carried out for 60 hours according to CEC F-020-98 (Keep-clean driving style) with fuel MIRO 95 octane E10 and engine oil RL 223 on a port-fuel-injector engine (M1 1 1 E) and the deposits on the Intake valves (internal valve deposits, IVD) determined. The formulations used are listed in Table 2, the results in Tables 3 and 4.

From Table 4 it can be seen that 40 mg / kg addition of the substances according to the invention (Formulation 10) are capable of producing comparable effect on the inlet valves, as in Comparative Formulation 9 a combination of 100 mg / kg detergent (Mannich PIBA) with 10 mg / kg dimer fatty acid for corrosion inhibition.

The compounds according to the invention are therefore similarly effective at lower dosages.

Table 2

PIBA: polyisobutene, M _n approx. 1000 g / mol

Mannich PIBA: Mannich product based on phenol (substituted with a polyisobutene, MN about 1000 g / mol), formaldehyde and dialkylamines according to WO 2015 028391 with an active content of 80%.

Table 3

Table 4

Claims

claims

Use of a reaction product comprising a quaternized nitrogen compound or a fraction thereof obtained from the reaction product by purification, containing a quaternized nitrogen compound, the reaction product being obtainable by

wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid as corrosion inhibitors in fuels which have a content of alkali metals and / or alkaline earth metals and / or zinc of at least 0.1 ppm by weight.

2. Use according to claim 1, characterized in that the alkali and / or alkaline earth metals and / or zinc selected from the group consisting of sodium, zinc, magnesium and calcium.

3. Use of a reaction product comprising a quaternized nitrogen compound or a fraction obtained therefrom from the reaction product by purification, containing a quaternized nitrogen compound, the reaction product being obtainable by

wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid as corrosion inhibitors in gasoline fuels.

4. Use of a reaction product comprising a quaternized nitrogen compound or a partial fraction thereof obtained from the reaction product by purification, containing a quaternized nitrogen compound, the reaction product being is available through

wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid in fuels to reduce corrosion of non-ferrous metals.

Use of a quaternized nitrogen compound-comprising reaction product or a quaternized nitrogen compound-containing partial fraction thereof obtained from the reaction product, which reaction product is obtainable by

wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid,

to improve the electrical conductivity and to prevent the electrostatic charge of fuels.

wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid, for the total or partial prevention of the formation of new deposits and / or total or partial removal of existing deposits on the fuels! n- and / or exhaust valves of petrol engines with port fuel injectors (PFI).

Use according to one of the preceding claims, characterized in that the quaternizable nitrogen compound is chosen from a) at least one alkylamine comprising at least one compound of the following general formula 3,

R _a R _b R _c N (3) where

at least one of the radicals R _a , Rb and R _c , such as one or two, is a straight-chain or branched, saturated or unsaturated C 8 -C 40 -hydrocarbyl radical (in particular straight-chain or branched Cs-C ₄ o-alkyl) and the remaining radicals are identical or different, straight-chain or branched, saturated or unsaturated C 1 -C 6 -hydrocarbyl radicals (especially C 1 -C 6 -alkyl);

d) at least one reaction product of a hydrocarbyl-substituted acylating agent and a compound containing a nitrogen or oxygen atom and additionally containing at least one quaternizable, in particular tertiary, amino group; and e) mixtures thereof.

Use according to any one of Claims 1 to 6, characterized in that the quaternizable nitrogen compound, e.g. is an alkylamine comprising at least one compound represented by the following general formula 3,

RaRbRcN (3) wherein all radicals R _a , Rb and R _{c are} identical or different straight-chain or branched, saturated or unsaturated C 8 -C ₄ o-hydrocarbyl radicals, in particular straight-chain or branched Cs - C ₄ o-alkyl radicals.

Use according to any one of the preceding claims, characterized in that the quaternizing agent comprises an epoxide of general formula 4

in which

the radicals Rd contained therein are the same or different and are H or a hydrocarbyl radical, where the hydrocarbyl radical is an aliphatic or aromatic radical having at least 1 to 10 carbon atoms.

Use according to any one of the preceding claims, characterized in that the free acid of the quaternizing agent is a hydrocarbyl-substituted C3-C28 dicarboxylic acid.

Use according to any one of the preceding claims, characterized in that the hydrocarbyl substituent of the carboxylic acid is a polyalkylene radical having a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25.

Use according to any one of the preceding claims, characterized in that the quaternizable tertiary amine is a compound of formula 3 wherein at least two of R _a , R b and R _{c are the} same or different and represent a straight or branched C 10 -C 20 alkyl radical and the rest of the radical is C 1 -C ₄ -alkyl.

Use according to Claim 9, characterized in that the quaternizing agent is chosen from lower alkylene oxides in combination with a hydrocarbyl-substituted polycarboxylic acid.

Use according to one of claims 1 to 3 or 6 to 13 for inhibiting the corrosion of iron, steel and / or non-ferrous metal surfaces.

15. Use according to one of claims 1, 2, 4, 5 or 7 to 14, characterized in that it is the fuel is a diesel or gasoline, preferably gasoline.