EP1957472A1

EP1957472A1 - Method for producing ionic liquids

Info

Publication number: EP1957472A1
Application number: EP06819480A
Authority: EP
Inventors: Kai Michael Exner; Klemens Massonne; Veit Stegmann; Matthias Maase
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-11-21
Filing date: 2006-11-15
Publication date: 2008-08-20
Also published as: CN101309914A; JP2009516720A; DE102005055815A1; US20080287684A1; WO2007057403A1; KR20080079271A

Abstract

The present invention relates to a method for producing ionic liquids [A]+n[Y]n- by reacting ionic liquids, the anion of which is a halogenide [A]+[X]-, with an acid H+n[Y]n-, wherein the formed hydrohalic acid is collected with an amine and the thus formed ammonium halide can be separated.

Description

Process for the preparation of ionic liquids

The present invention describes a process for the preparation of ionic liquids (I) by reacting ionic liquids whose anion is a halide (II) with an acid (IM), wherein the generated hydrohalic acid is trapped with an amine and the resulting Ammonium halide can be separated.

Ionic liquids gain as a solvent, e.g. in the implementation of chemical reactions increasingly important. For example, P. Wasserscheidt in chemistry in our time 37, 52 (2003) gives an overview of the use of ionic liquids in multiphase catalysis. However, other applications have also been proposed, such as e.g. their use in extraction or separation processes, as heat transfer, etc.

In all these applications, the purity of the ionic liquids used is important. For example, impurities can affect the course of chemical reactions. For example, P. Tyson et al (Electrochemical Society Proceedings, Vol. 99-41, 161) have pointed out problems with the use of chloride-containing ionic liquids in liquid-phase hydrogenation and Suzuki coupling. Therefore, high demands must be placed on their purity in the production of ionic liquids.

Frequently, ionic liquids are prepared by quaternization of the corresponding nitrogen or phosphorus compounds, alkyl halides generally being used as alkylating reagents. The ionic liquids thus obtained can then be used themselves as solvents, etc. However, these also serve as starting material for the preparation of ionic liquids whose anion is unlike a halide, by, by the so-called metathesis reaction, the anion is exchanged. In this case, however, the problem frequently arises that the resulting ionic liquid still contains traces of halide, which, as described above, can lead to problems in use as a solvent, etc. Or the separation of the halide traces requires high technical complexity, which causes high operating costs and / or investment costs and thus severely affects the efficiency of a process. As an example, here the speckling of ionic liquids containing HCl, called here, because sometimes days of stripping times must be taken into account.

The object of the present invention is therefore to provide a technically usable process for the production of ionic liquids, in particular with a reduced halide content. It has been found that ionic liquids of the formula (I)

[A] ⁺ _n [Y] ⁿ - (I)

in which

[A] ⁺ for a quaternary nitrogen heterocycle cation, oxonium cation, sulfonium cation or phosphonium cation;

n is 1, 2, 3 or 4; and

[Y] ^p - for an anion selected from the group of sulfates, sulfites and sulfonates, the group of phosphates, the group of phosphonates and phosphinates, the group of phosphites, the group of phosphonites and phosphinites, the group of carboxylic acids, or

NO ₃ -;

stand;

obtained by reacting an ionic liquid of the formula (II)

[A] ⁺ [X] - (II)

in which

[A] ^{+ has} the meaning given above; and

[X] - fluoride, chloride, bromide or iodide;

mean;

with an acid of formula IM

H ⁺ _n [Y] ⁿ - (IM)

where n and [Y] ⁿ - have the abovementioned meaning;

reacted; wherein, the forming acid of formula IV

H ⁺ [X] - (IV)

where [X] ^"has the meaning given above;

with an amine of the formula V

NR ¹ R ¹ R ³ (V)

in which

R ¹ , R ² and R ³ independently of one another represent hydrogen or C 1 -C 20 -alkyl which may optionally be substituted, the number of carbon atoms of the radicals R ¹ , R ² and R ³ together being at least 10;

mean;

intercepted;

and the resulting ammonium halide of formula VI

[HNR ¹ R ² R ³ I ⁺ [X] - (VI)

wherein the radicals X, R ¹ , R ² and R ^{3 have} the abovementioned meaning;

is separated.

The reaction of the ionic liquid of the formula II with the acid of the formula III is usually carried out at a temperature of -50 ° C. to 150 ° C., especially at -20 to 120 ° C., in particular at 0 to 100 ° C., preferably at 20 to 60 ° C performed.

As a rule, the reaction takes place at normal pressure.

Usually, the ionic liquid of the formula II and the acid of the

Formula IM used in the stoichiometric ratio. It may also be beneficial to use one or the other component in excess on a case-by-case basis.

In general, the amine of the formula V is used with respect to the acid of the formula IM in the stoichiometric ratio or in excess. In one embodiment, the amine is used in the stoichiometric ratio. In another embodiment, the amine of formula V is in excess, preferably in the range of 1, 5 to 2.5 times, in particular in the range of 1, 8 to 2.2 times the stoichiometric ratio used. In a further embodiment, in which the amine is continuously regenerated, it is also possible to use the amine in a deficit based on a snapshot.

From case to case, it may be advantageous to perform the inventive method in substance.

It is also possible to work in the presence of a solvent. Suitable solvents are those in which the ammonium halide of the formula VI dissolves or does not dissolve the ionic liquid of the formula I. For this example, aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene or p-XyIoI, chlorinated aromatic hydrocarbons such as chlorobenzene, or cyclic hydrocarbons such as cyclohexane, suitable.

Usually, the amine of the formula V is selected such that it itself or the ammonium halide of the formula VI formed is not or only to a small extent dissolved in the ionic liquid of the formula I. The solubility of the amine of the formula V or of the ammonium halide of the formula VI in the ionic liquid of the formula I is preferably in each case within a range of less than 10%, especially less than 5%, in particular less than 2% (expressed as the molar ratio between the amine or Ammonium halide and the ionic liquid). This is especially true in the case when working without solvent.

In a further embodiment, which applies especially in the case that is carried out in the presence of a solvent, the amine of the formula V is selected so that it and the ammonium halide of the formula VI formed are more soluble in the solvent used than in the ionic liquid of the formula I.

The separation of the reaction products of the formula I and VI takes place via liquid-liquid phase separation.

In one embodiment of the present invention, one works without solvent.

In this case, the ionic liquid of the formula II, the acid of the formula III and the amine of the formula V are combined and the mixture is brought to the desired temperature. After completion of the implementation, the

Phases separated. One phase contains the ionic liquid of the formula I and the other phase is the formed ammonium halide of formula VI and optionally unreacted amine of formula V (if used in excess).

In one particular embodiment, the amine of formula V is added to the reaction mixture in two or more portions, the phases of the reaction mixture being able to be separated before the additional addition of amine and the ammonium halide of formula VI and, if appropriate, unreacted amine of the formula V being removed can be.

In a further embodiment, the ionic liquid of the formula II and the acid of the formula III are combined. After completion of the reaction, the amine of formula V is added and again after completion of the ammonium halide formation, the phases are separated. One phase contains the ionic liquid of the formula I and the other phase the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess). It may be advantageous in this case to bring the initially introduced mixture of ionic liquid of the formula II and acid of the formula III to the desired temperature. But it is also possible the desired temperature after addition of the amine

To set formula V.

In a particular embodiment, in this case the amine of the formula V is added to the reaction mixture in two or more portions, the phases of the reaction mixture being separated before the further addition of amine and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V being removed ,

In a further embodiment, the ionic liquid of the formula II is initially charged and the acid of the formula III and the amine of the formula V are added in parallel. After completion of the reaction, the phases are separated. One phase contains the ionic liquid of the formula I and the other phase the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess). It may be advantageous to bring the ionic liquid of the formula II to the desired temperature. However, it is also possible to set the desired temperature after addition of the acid of the formula III and of the amine of the formula V.

Again, it may be advantageous to interrupt the dosing, perform a meantime phase separation and separated ammonium halide of formula VI and optionally unreacted amine of formula V (if this is used in excess) to separate. In a further embodiment of the present invention, the separation of the phases is carried out in the presence of a solvent. In this case, the reaction mixtures, which are described in the embodiments without solvent, are mixed with a solvent before the phase separation and then the phases are separated. One phase contains the ionic liquid of the formula I and the other phase contains the solvent and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess).

It may be advantageous here to add the solvent in two or more portions and to separate off the corresponding phases according to the principles of extraction known to the person skilled in the art.

In a particular embodiment, the first phase separation is carried out in the absence of a solvent and then extracted with the solvent.

In a further embodiment of the present invention, the representation of the ionic liquid of the formula I is carried out in the presence of a solvent.

Here, the ionic liquid of the formula II, the acid of the formula IM, the amine of the formula V and the solvent are combined and brought the mixture to the desired temperature. After completion of the reaction, the phases are separated. One phase contains the ionic liquid of the formula I and the other phase contains the solvent and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess).

In a particular embodiment, in this case only a part of the solvent is added to the educts and the other part for the separation of the ammonium halide of the formula VI and the optionally unreacted amine of the formula V (if this is used in excess). used.

In a further particular embodiment, in this case the amine of the formula V is added to the reaction mixture in two or more portions, optionally in the solvent, the phases of the reaction mixture being separated before the additional addition of amine and the solvent and the ammonium halide formed Formula VI and possibly unreacted

Amine of formula V are separated. In a further embodiment, the ionic liquid of the formula II and the acid of the formula III are combined. After completion of the reaction, the amine of formula V and the solvent is added and again after completion of the ammonium halide formation, the phases are separated. One phase contains the ionic liquid of the formula I and the other phase contains the solvent and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess). It may be advantageous in this case to bring the initially introduced mixture of ionic liquid of the formula II and acid of the formula III to the desired temperature. But it is also possible to set the desired temperature after addition of the amine of formula V.

In a particular embodiment, in this case only a part of the solvent is added to the amine of the formula V and the other part for the separation of the ammonium halide of the formula VI and the optionally unreacted

Amine of formula V (if used in excess).

In a further particular embodiment, in this case the amine of formula V is added to the reaction mixture in two or more portions, the phases of the reaction mixture being separated before the further addition of amine and ammonium halide of formula VI and optionally unreacted amine of formula V removed become.

In a further embodiment, the ionic liquid of the formula II is initially charged and the acid of the formula III and the amine of the formula V are added in parallel. In this case, the acid of the formula III and / or the amine of the formula V are metered into the solvent. After completion of the reaction, the phases are separated. One phase contains the ionic liquid of the formula I and the other phase contains the solvent and the ammonium halide of the formula VI formed and optionally unreacted amine of the formula V (if this is used in excess). It may be advantageous to bring the ionic liquid of the formula II to the desired temperature. However, it is also possible to set the desired temperature after addition of the acid of the formula III and of the amine of the formula V.

In a particular embodiment, in this case only a part of the solvent is added to the acid of the formula III and / or the amine of the formula V and the other part for the separation of the ammonium halide of the formula VI and the optionally unreacted amine of the formula V (if this used in excess). Again, it may be advantageous to interrupt the dosing, perform an intermediate phase separation and separated ammonium halide of the formula VI and optionally unreacted amine of the formula V (if this is used in excess) to separate.

The preparation of the ionic liquid of the formula I can be carried out batchwise, continuously or in a semi-batch mode. Adjusted accordingly, the separation of the resulting ammonium halide of the formula VI.

The liquid-liquid phase separation takes place, for example, by such techniques as described in Ullmann's Encyclopedia of Industrial Chemistry, sixth edition, 2000 electronic release, chapter "Liquid-Liquid Extraction", in particular in subchapter 4 "Phase-Separation Equipment" , are described; preferably by decanting, phase separators, centrifuging or mixer-settler apparatuses, and particularly preferably by phase separators.

It may furthermore be advantageous to recover the amine of the formula V used from the ammonium halide of the formula VI formed and, if desired, to use it again in the process according to the invention for the preparation of the ionic liquids of the formula I.

The recovery of the amines of formula V can be carried out, for example, by reacting the ammonium halide of the formula VI with a strong base, for example NaOH, KOH, Ca (OH) ₂ , lime, Na ₂ CO ₃ , NaHCO ₃ , K ₂ CO ₃ , or KHCO ₃ , optionally in a solvent such as water, methanol, ethanol, n- or iso-propanol, n-butanol, n-pentanol or butanol or pentanol isomer mixtures or acetone releases.

In a preferred embodiment of the invention, the strong base is used in a very concentrated solution, particularly preferably an aqueous solution, for example at least 5% by weight, preferably at least 10% by weight and more preferably at least 15% by weight. ig.

The amount of base usually chosen according to the stoichiometry. From case to case it may be beneficial to use a deficit or surplus. As a rule, equimolar is used.

If the preparation of the ionic liquid of the formula I was carried out in the absence of a solvent, then the amine of the formula V, if it forms a separate phase, can be separated off or else be removed from the mixture by distillation. If necessary, the amine of formula V can be separated by extraction with an extractant. As extraction agent, conventional solvents such as aliphatic ethers, for example diethyl ether or methyl tert-butyl ether, cyclic ethers such as tetrahydrofuran, 1, 3-dioxane or 1, 4-dioxane, hydrocarbons such as pentane, hexane, cyclopopentane or cyclohexane, aromatic hydrocarbons such as Benzene, toluene, o-xylene, m-xylene or p-xylene, chlorinated hydrocarbons such as methylene chloride, chloroform or 1, 2-dichloroethane or chlorinated aromatic hydrocarbons such as chlorobenzene into consideration.

If necessary, the amine of formula V may be further purified before reuse, e.g. by distillation.

If a solvent is used in the preparation of the ionic liquid of the formula I, the amine of the formula V can be obtained by treating the solution of the ammonium halide of the formula VI with the abovementioned bases and the liberated amine of the formula V with the appropriate solution - Are extracted medium in the manner known to those skilled and the amine of the formula V by conventional methods, such as Distillation be recovered.

The purification can be carried out, for example, by washing once or several times, drying, filtering, stripping, distilling and / or rectifying.

Dried can e.g. by removal of water which may be present by means of distillation or azeotropic distillation with benzene, toluene, xylene, butanol or cyclohexane.

Filtration may be useful, for example, to remove precipitated solids or to eliminate any coloration, for example, by filtration over activated carbon, alumina, Celite or silica gel.

A distillation, for example for the removal of optionally contained solvent, can preferably via a falling or thin film evaporator, optionally under vacuum, carried out, to improve the separation of a column can be placed.

Accordingly, the solvent used can, if necessary, be purified and reused if desired.

Another object of the present invention is thus a process for the preparation of ionic liquids of the formula I, comprising the following steps:

Reaction of an ionic liquid of the formula II with an acid of the formula III; Scavenging the forming acid of formula IV with an amine of formula V;

Separation of the formed ionic liquid of the formula I and of the ammonium halide of the formula VI formed by liquid / liquid phase separation;

Adding a base to the phase containing the formed ammonium halide of formula VI and releasing the amine of formula V;

optionally purification of the crude amine of formula V; and

if appropriate, recycling of the optionally purified amine for reaction with an ionic liquid of the formula II with an acid of the formula III.

In a preferred embodiment, the ionic liquid of the formula II and the acid of the formula III are initially charged and the mixture is extracted continuously with the amine of the formula V, the free amine being regenerated continuously from the separated ammonium halide or the ammonium halide / amine and the Extraction process is fed back. In this case, based on a snapshot of the extraction part, the amine can be used in molar excess with respect to the free acids. The extraction can be assisted by a solvent or can also be carried out completely continuously, the amine phase and the phase with the ionic liquid being continuously conducted past one another.

Preferably, the ionic liquids of the formula I and M, and the ammonium halide of the formula VI independently of one another have a melting point of less than 180 ° C. Furthermore, the melting point in a range from - 50 ° C to 150 ° C, preferably in a range of -20 ° C to 120 ° C and preferably below 100 ⁰ C.

Preferably, ionic liquids of the formula I are prepared which have a molecular weight of less than 1000 g / mol, preferably less than 500 g / mol, in particular less than 250 g / mol.

Preferably, ionic liquids of the formula I are prepared in which the variables, taken alone and in combination, have the following meanings:

[A] + is a cation selected from the compounds of the formulas (Ia) to (Iv),

(Ia) (Ib) (Ic)

(Id) (Ie) (If)

(Ii) (Ij) (Ij ')

(Ik) (Ik ') (H)

(Im) (In) (In)

(Ip) (Iq) (Iq ')

(Iq ") (Ir) (Ir ')

(Ir ") (Is) (It)

R ^b R ^b

R-P-R S-R

I i

R R

(Iu) (Iv)

In the abovementioned formulas (Ia) to (Iv)

• the radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms; and

• the radicals R ^a to R ^{1 are} independently hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 1 to 20 carbon atoms, wherein the radicals R ^a to R ¹ , which in the abovementioned formulas (I) are bonded to a carbon atom (and not to a heteroatom), can additionally also stand for halogen or a functional group; or

two adjacent radicals from the series R ^a to R ¹ together also for a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Residue with 1 to 30 carbon atoms.

Heteroatoms in the definition of the radicals R and R ^a to R ^{1 are in} principle all heteroatoms in question, which are capable of formally a -CH 2 -, a - CH =, replace a -C≡ or a = C = group. When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. Particular preferred groups are -O-, -S-, -SO-, -SO ₂ -, -NR'-, -N =, -PR'-, -PR ' ₂ and -SiR' ₂ - called, where the radicals R 'are the remainder of the carbon-containing radical. The radicals R ^a to R ¹ can be present in the cases where they are bonded in the above formulas (I) to a carbon atom (and not to a heteroatom), also be bound directly via the heteroatom.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. Suitable examples are -OH (hydroxy), = 0 (especially as a carbonyl group), -NH ₂ (amino), = NH (imino), -COOH (carboxy), -CONH ₂ (carboxamide), -SO3H (Sulfo) and -CN (cyano) called. Fractional groups and heteroatoms may also be directly adjacent so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide ) or -CONR'- (tertiary amide), are included, for example, di (Ci-C4-alkyl) amino, Ci-C4-alkyloxycarbonyl or C1-C4alkyloxy.

Halogens are fluorine, chlorine, bromine and iodine.

The radical R preferably stands for

• straight-chain or branched, unsubstituted or monosubstituted to hydroxyl, halogen, phenyl, cyano, C 1 -C 6 -alkoxycarbonyl and / or sulfonic acid-substituted C 1 -C 20 -alkyl having in total 1 to 20 carbon atoms, for example methyl, ethyl, 1 Propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3 Pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2- pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2- Ethyl 1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxy-car bonyl) -ethyl, 2- (n-butoxy-carbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid; Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C 1 to C 1 alkyl as end group, such as R ^A O- (CHR ^B -CH ₂ -O) _m -CHR ^B -CH ₂ - or R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ θ) _m -CH ₂ CH ₂ CH ₂ CH ₂ θ- with R ^A and R ^B preferred

Is hydrogen, methyl or ethyl and m is preferably 0, 12 or 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9- Trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;

• vinyl; and

N ₁ N-Di-Cr to C 6 -alkyl-amino, such as N, N-dimethylamino and N, N-diethylamino.

Particularly preferably, the radical R is unbranched and unsubstituted Cr to Cis-alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, especially for methyl, ethyl, 1-butyl and 1-octyl and also for CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - and CH ₃ CH ₂ O- ( CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - with m equal to 0, 1 2 or 3.

The radicals R ^a to R ¹ are preferably each independently

• hydrogen;

• halogen;

• a functional group;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups cis-alkyl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C2-Ci8- alkenyl; Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-C12-

cycloalkyl;

Optionally C5-C12 cycloalkenyl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles; or

• an optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five to six-membered, oxygen, nitrogen and / or sulfur atoms pointing heterocycle; or

two adjacent radicals together for an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted ring.

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles d- to cis-alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2 Butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3 Methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1 pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3- Dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl, cyclopentylmethyl, 2-

Cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, α, α-dimethylbenzyl, p- Tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- Butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, methoxy, ethoxy, formyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2- Methyl 1, 3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-amino ethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3 Dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, acetyl, C _m F 2 ( _m -a) + (ib) H2a + b with m equal to 1 to 30,

0 <a <m and b = 0 or 1 (for example CF3, C2F5, CH2CH2-C _(m-2) F2 (m-2) + i, C ₆ Fi _3, C ₈ Fi _7, C10F21, C ₂ F ₂₅ ), Chloromethyl, 2-chloroethyl, trichloromethyl, 1, 1-dimethyl-2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxy-isopropyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8- Hydroxy-3,6-dioxa-octyl, 1-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 1-hydroxy-4,8-dioxa-undecyl, 15- Hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-dioxetetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3, 6-dioxo-octyl, 1 1-methoxy

3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy 5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 1-ethoxy-3,6, 9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 1-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa nonyl or 14-

Ethoxy-5,10-oxa-tetradecyl.

In optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C2-C18 - Alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F2 ( _m -a) - (ib) H2a-b with im <30, 0 <a <m and b = 0 or 1.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles Ce- to Ci2-aryl is preferably phenyl, ToIyI, XyIyI, α-naphthyl, ß-naphthyl, 4-diphenylyl , Chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-

Propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, Chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C6F ( ₅ - _a ) H _a with 0 <a <5.

In the case of optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles Cs to Ci2-cycloalkyl is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl , Dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F 2 ( _m -a) - (ib) H 2a-b with im <30, 0 <a <n and b = 0 or 1 and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles Cs to Ci2-cycloalkenyl is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2.5 Cyclohexadienyl or C _m F 2 ( _m -a) -3 (ib) H 2a-3b with m <30,

0 <a <m and b = 0 or 1.

In one optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms

Heterocycle is preferably furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.

Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more several substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3- propylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1, 3-propenylene, 1-Ci-C ₄ -AlkVl 1-aza-1, 3-propenylene, 1,4-buta-1,3-dienylene, 1-aza-1, 4-buta-1,3-dienylene or 2-aza-1,4-buta-1 , 3-dienylene. If the abovementioned radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.

If the abovementioned radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.

The radicals R ^a to R ¹ are particularly preferably each independently

• hydrogen;

• straight-chain or branched, unsubstituted or monosubstituted to hydroxyl, halogen, phenyl, cyano, C 1 -C 6 -alkoxycarbonyl and / or sulfonic acid-substituted C 1 -C 20 -alkyl having in total 1 to 20 carbon atoms, for example methyl, ethyl, 1 Propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3 Pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2- Hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl 2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1 Dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxy- approx carbonyl) ethyl, 2- (n-butoxy-carbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, naphtha-butyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;

Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C 1 to C 1 alkyl as end group, such as R ^A O- (CHR ^B -CH ₂ -O) _m -CHR ^B -CH ₂ - or R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ θ) _m -CH ₂ CH ₂ CH ₂ CH ₂ θ- with R ^A and R ^{B is} preferably hydrogen, methyl or ethyl and m is preferably 0, 1, 2 or 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl , 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9, 12-tetraoxatridecyl and 3,6,9,12-

Tetraoxatetradecyl; • vinyl; and

• N ₁ N-di-Ci- to C 6 -alkyl-amino, such as N, N-dimethylamino and N, N-diethylamino.

Most preferably, the radicals R ^a to R ¹ independently of one another are hydrogen or C 1 - to C 6 -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl Phenyl, for 2-hydroxyethyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-

Butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N-diethylamino, for chlorine and for CHaCKCHaCHaCVCHaCHa and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - with m being equal to 0, 1 2 or 3.

Very particularly preferred pyridinium ions (Ia) are those in which

• one of the radicals R ^a to R ^{e is} methyl, ethyl or chlorine and the remaining radicals R ^a to R ^{e are} hydrogen;

• R ^{c is} dimethylamino and the remaining radicals R ^a , R ^b , R ^d and R ^{e are} hydrogen;

• all radicals R ^a to R ^{e are} hydrogen;

R ^{b is} carboxy or carboxamide and the remaining radicals R ^a , R ^b , R ^d and R ^{e are} hydrogen; or

• R ^a and R ^b or R ^b and R ^{c is} 1, 4-buta-1, 3-dienylene and the remaining radicals R ^a , R ^b , R ^c and R ^{d are} hydrogen;

and in particular those in which

• R ^a to R ^{d are} hydrogen; or

• one of the radicals R ^a to R ^{e is} methyl or ethyl and the remaining radicals R ^a to R ^{e are} hydrogen.

As very particularly preferred pyridinium ions (IVa) may be mentioned 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1

Octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl ) -pyridinium, 1,2-di- methylpyridinium, i-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1 Dodecyl) -2-methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1 Butyl) - 2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium,

1- (1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1, 2-dimethyl-5-ethylpyridinium, 1, 5-diethyl-2-methylpyridinium, 1- (1-butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium and (1-Octyl) -2-methyl-3-ethylpyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethyl- pyridinium and 1-

(1-hexadecyl) -2-methyl-3-ethyl-pyridinium.

Very particularly preferred pyridazinium ions (Ib) are those in which

• R ^a to R ^{d are} hydrogen; or

• one of the radicals R ^a to R ^{d is} methyl or ethyl and the remaining radicals R ^a to R ^{d are} hydrogen.

Very particularly preferred pyrimidinium ions (Ic) are those in which

R ^{a is} hydrogen, methyl or ethyl and R ^b to R ^{d are} independently hydrogen or methyl; or R ^{a is} hydrogen, methyl or ethyl, R ^b and R ^{d are} methyl and R ^{c is} hydrogen.

Very particularly preferred pyrazinium ions (Id) are those in which

R ^{a is} hydrogen, methyl or ethyl and R ^b to R ^{d are} independently hydrogen or methyl;

R ^{a is} hydrogen, methyl or ethyl, R ^b and R ^{d are} methyl and R ^{c is} hydrogen; • R ^a to R ^{d are} methyl; or

• R ^a to R ^{d are} methyl.

Very particularly preferred imidazolium ions (Ie) are those in which R ^{a is} hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R ^b to R ^{d are} independently hydrogen, methyl or ethyl ,

As very particularly preferred imidazolium ions (IVe) may be mentioned 1-

Methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1 Hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1 -Hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3- ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl-1-S-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3 ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) 3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1, 2-dimethylimidazolium, 1, 2,3- Trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) - 2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1, 4,5-trimethylimidazolium, 1, 3,4,5-tetramethylimidazolium, 1, 4,5-trimethyl-3-ethylimidazolium, 1, 4,5-trimethyl-3-butylimidazolium and 1, 4,5-trimethyl-3-one octylimidazolium.

Very particularly preferred pyrazolium ions (If), (Ig) or (Ig ') are those in which

• R ^{a is} hydrogen, methyl or ethyl and R ^b to R ^{d are} independently hydrogen or methyl.

Very particularly preferred pyrazolium ions (Ih) are those in which

• R ^a to R ^{d are} independently hydrogen or methyl.

Very particular preference is given to using as 1-pyrazolinium ions (Ii) those in which

• independently R ^a to R ^{f are} hydrogen or methyl. Very particular preference is given to using 2-pyrazolinium ions (Ij) or (Ij ') as those in which

• R ^{a is} hydrogen, methyl, ethyl or phenyl and R ^b to R ^{f are} independently hydrogen or methyl.

Very particular preference is given to using as 3-pyrazolinium ions (Ik) or (Ik ') those in which

• R ^a and R ^{b are} independently hydrogen, methyl, ethyl or phenyl and R ^c to R ^{d are} independently hydrogen or methyl.

Very particularly preferred imidazolinium ions (II) are those in which

• R ^a and R ^{b are} independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R ^c and R ^{d are} independently hydrogen, methyl or ethyl, and R ^e and R ^{f are} independently hydrogen or methyl.

Very particular preference is given to using imidazolinium ions (Im) or (Im ') as those in which

• R ^a and R ^{b are} independently hydrogen, methyl or ethyl and R ^c to R ^{f are} independently hydrogen or methyl.

Very particular preference is given to using imidazolinium ions (In) or (In ') as those in which

• R ^a to R ^{c are} independently hydrogen, methyl or ethyl and R ^d to R ^{f are} independently hydrogen or methyl.

Very particular preference is given to using as thiazolium ions (lo) or (lo ') and as oxazolium ions (Ip) those in which

• R ^{a is} hydrogen, methyl, ethyl or phenyl, and R ^b and R ^{c are} independently hydrogen or methyl.

Very particular preference is given to using as 1,2,4-triazolium ions (Iq), (Iq ') or (Iq ") those in which • R ^a and R ^{b are} independently hydrogen, methyl, ethyl or phenyl and R ^{c is} hydrogen, methyl or phenyl.

Very particular preference is given to using as 1,2,3-triazolium ions (Ir), (Ir ') or (Ir ") those in which

• R ^{a is} hydrogen, methyl or ethyl and R ^b and R ^{c are} independently hydrogen or methyl, or R ^b and R ^c together are 1, 4-buta-1, 3-dienylene.

Very particularly preferred pyrrolidinium ions (Is) are those in which

• R ^{a is} hydrogen, methyl, ethyl or phenyl and R ^b to R ^{1 are} independently hydrogen or methyl.

Very particular preference is given to imidazolidinium ions (It) as those in which

• R ^a and R ^{d are} independently hydrogen, methyl, ethyl or phenyl and R ^b and R ^c and R ^e to R ^{h are} independently hydrogen or methyl.

Very particularly preferred as phosphonium ions (Iu) are those in which

R ^a to R ^c independently of one another are C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.

Among the above-mentioned heterocyclic cations, the pyridine ions, pyrazolinium, pyrazolium ions, and imidazolinium and imidazolium ions are preferable.

Particularly preferred are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium,

1- (1-Octyl) pyridinium, 1- (1-dodecyl) pyridinium, 1- (1-tetradecyl) pyridinium, 1- (i-hexadecyl) pyridinium, 1, 2-dimethylpyridinium, 1-ethyl 2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2- methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium,

1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl ) -2-ethylpyridinium, 1- (1 Tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1, 2-dimethyl-5-ethyl-pyridinium, 1, 5-diethyl-2-methylpyridinium, 1- (1-butyl) 2-methyl-3-ethyl-pyridinium, 1- (1-hexyl) -2-methyl-3-ethyl-pyridinium, 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1 - ( 1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethylpyridinium, 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium , 1-

Methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1 Hexadecyl) imidazolium, 1, 3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1, 2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2, 3-dimethylimidazolium and 1- (1-octyl) -2,3-dimethylimidazolium, 1, 4-dimethylimidazolium, 1, 3,4-trimethylimidazolium, 1, 4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1, 4-dimethyl-3-octylimidazolium, 1, 4,5-trimethylimidazolium, 1, 3,4,5-tetramethylimidazolium, 1, 4,5-trimethyl-3-ethylimidazolium, 1, 4,5-trimethyl-3 butylimidazolium and 1, 4,5-trimethyl-3-octylimidazolium.

[Y] ⁿ "is an anion selected

The group of sulfates, sulfites and sulfonates of the general formula: SO ₄ ^{2 "} , HSO ₄ -, SO ₃ ^2" , HSO ₃ -, R ^{A #} OSO ₃ -, R ^{B #} SO ₃ -;

The group of phosphates of the general formula PO ₄ ^{3 "} , HPO ₄ ^2" , H ₂ PO ₄ -, R ³ PO ₄ ^{2 "} , HR ^{A #} PO ₄ -, R ^{A #} R ^{B #} PO ₄ -;

The group of phosphonates and phosphinates of the general formula: R ^{A #} HPO ₃ -, R ^{A #} R ^{B #} PO ₂ -, R ^{A #} R ^{B #} PO ₃ -;

The group of phosphites of the general formula: PO ₃ ^{3 "} , HPO ₃ ^2" , H ₂ PO ₃ -, R ³ PO ₃ ^{2 "} , R ^{A #} HPO ₃ -, R ^{A #} R ^{B #} PO ₃ -; Phosphonites and phosphinites of the general formula:

R ^{A #} R ^{B #} po ₂ -, R ^{A #} HPO ₂ -, R ^{A #} R ^{B #} PO-, R ^A HPO ";

• the group of carboxylic acids of the general formula: R ^{A #} COO-;

• NO ₃ -;

In which R ^{A #} and R ^{B #} are each independently hydrogen, C ₁ -C 30 -alkyl, optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C ₂ - Ci8-alkyl, C6-Ci ₄ -aryl, Cs-Ci ₂ - cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or

Sulfur-containing heterocycle, wherein two of them together an unsaturated, saturated or aromatic, optionally by a or several oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups can form interrupted ring, wherein the radicals mentioned in each case additionally by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles len may be substituted.

Therein, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C1-C18 alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl , Hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl,

Dodecyl, tetradecyl, hexadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethyl-ibutyl, 1, 1, 3, 3-tetramethylbutyl, benzyl, 1-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, C _m F 2 (ma) + (ib) H 2 a + b is equal to 1 to 18, 0 <a <m and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C (m-2) F ₂ (m-2) ₊ i, C ₆ Fi _3, C ₈ Fi _7, C10F21, C ₂ F _25), chloromethyl, 2-chloroethyl, trichloromethyl, 1, 1-dimethyl-2-chloroethyl, 2-methoxy carbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1 , 2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1, 3-dioxolan-2-yl, 1, 3-dioxan-2-yl, 2 -Methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyl-oxyethyl, chloromethyl, trichloromethyl, trifluoromethyl, 1 , 1-dimethyl-2-chloroethyl, 2-methoxy-isopropyl, 2-ethoxy-ethyl , Butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl,

4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylamino-butyl, 6- Dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or ö-ethoxyhexyl.

Optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted I- minogruppen interrupted C2-Cis-alkyl, for example, 5-hydroxy-3 oxapentyl, 8-hydroxy-3,6- dioxaoctyl, 1 1-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 1 1-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9- Hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxa-octyl, 1-methoxy-3,6,9-trioxaundecyl , 7-

Methoxy-4-oxaheptyl, 1-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl , 5-ethoxy-3- oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 1-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 1-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4, 8,12-tιϊoxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl.

If two radicals form a ring, these radicals can be taken together, for example, as fused radical 1, 3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa -1, 3-propenylene, 1-aza-1, 3-propenylene, 1-C 1 -C 4 -alkyl-1-aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza -1,4-buta-1,3-dienylene or 2-aza-1,4-buta-1,3-dienylene.

The number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or of the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.

Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.

The term "functional groups" is to be understood as meaning, for example, the following: carboxy, carboxamide, hydroxy, di- (C 1 -C ₄ -alkyl) amino, C 1 -C ₄ -alkyloxycarbonyl, cyano or C 1 -C ₄ -alkoxy, where C 1 to C ₄ -Alkyl methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

Optionally C6-C4-aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles are, for example, phenyl, ToIyI, XyIyI, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, Dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6- Dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or E-thoxymethylphenyl.

Optionally C5-C12-cycloalkyl which is substituted by functional groups, aryl, alkyl, aryloxy, halogen, heteroatoms and / or heterocycles are, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, Butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

A five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle is, for example, furyl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxifuryl, dimethoxypyridyl , Diflorurpyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.

Preferred anions are selected from the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates, in particular selected from the group of sulfates, the group of carboxylic acids and the group of sulfonates or NO3 ^" .

Particularly preferred are SO ₄ ^{2 "} 'HSO ₄ ^" ; Ci-C ₄ alkyl-COO ^', particularly acetate and propionate, preferably acetate; Ci-C ₄ ^{haloalkyl-COO',} in particular trifluoroacetate, or perfluoropropionate, preferably trifluoroacetate; C 1 -C ₄ -alkyl-SO 3 ^" , preferably methylsulfonate, ethylsulfonate or butylsulfonate, preferably methylsulfonate; or C 1 -C ₄ -haloalkyl-SO 3 ^" , preferably trifluoromethylsulfonate or perfluoroethylsulfonate, preferably trifluoromethylsulfonate.

Very particularly preferred are SO ₄ ² "'HSO ₄ ", acetate and methyl sulfonate.

In a preferred embodiment, ionic liquids of the formula II are used in which the variables [A] ⁺ as defined for the ionic liquids of the formula I and X ^'is chloride or bromide, preferably represents CHIO chloride. The preferences for [A ] ⁺ apply accordingly.

In a preferred embodiment, amines of the formula V are used in which the radicals

• R ¹ to R ^{3 are} independently of each other Ci-Cis-alkyl; or

• R ¹ and R ² together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R ^{3 is} d-Cis-alkyl, 2-hydroxyethyl or 2-cyanoethyl.

and the number of carbon atoms of the radicals R ¹ , R ² and R ³ together is at least 10 but at most 30. In a further embodiment, amines of the formula V are used in which the radicals

• One of the radicals R ¹ to R ^{3 is} hydrogen and the other two radicals independently of one another are C 1 -C 6 -alkyl;

and the number of carbon atoms of R ² and R ³ together is at least 10 but not more than 30.

In a particular embodiment, diethyl-hexylamine, diethyloctylamine, diethyl (2-ethylhexyl) -amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di n-propyl- (2-ethylhexyl) -amine, di-isopropyl-butylamine, diisopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, di-isopropyl-2-ethylhexylamine, di-n -butylethylamine, di-n-butyl-n-propylamine, di-n-butyl-n-pentylamine, di-n-butylhexylamine, di-n-butyloctylamine, di-n-butyl (2-ethylhexyl) amine, dioctylamine , Diethyl-ethylamine, dinonylamine, tri-pentylamine, trihexylamine, trioctylamine, trinonylamine, tridecylamine, methyl-di- (2-ethylhexyl) -amine, ethyl-di- (2-ethylhexyl) -amine, propyl-di- (2-ethylhexyl) amine, butyl-di (2-ethylhexyl) amine, isopropyl-di- (2-ethylhexyl) amine, isobutyl-di- (2-ethylhexyl) -amine or tris (2-ethylhexyl) -amine, preferably Diethyl-hexylamine, diethyloctylamine, diethyl- (2-ethylhexyl) -amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylh exylamine, di-n-propyloctylamine, di-n-propyl- (2-ethylhexyl) -amine, di-isopropyl-butylamine, di-isopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, diisopropyl- (2 ethylhexyl) amine, di-n-butylethylamine, di-n-butyl-n-propylamine, di-n-butyl-n-pentylamine, di-n-butylhexylamine, di-n-butyloctylamine, di-n-butyl (2-ethylhexyl) amine, dioctylamine, diethyl- ethylamine, dinonylamine.tripentylamine, trihexylamine, trioctylamine, trinonylamine or tridecylamine.

The present invention is further illustrated by the following examples Example 1

13.1 1 g of 1-butyl-3-methyl-imidazolium chloride (75 mmol), 7.247 g (75 mmol) of methanesulfonic acid, 42.1 1 g of trihexylamine (150 mmol) were heated in 42.1 1 g of toluene at 40 ° C. , After stirring for about 1 h, the mixture was cooled to room temperature and the phases which formed were separated. The lower phase is dried at 80 ° C and a pressure of 10 mbar. 14.4 g of butyl 3-methylimidazolium methylsulfonate (containing 3.3% by weight of chloride) were obtained.

Example 2

8.74 g of 1-butyl-3-methyl-imidazolium chloride (50 mmol), 3.00 g (50 mmol) of acetic acid (99%), 28.00 g of trihexylamine (100 mmol) were heated to 40 ° C. in 28 g of toluene. After stirring for about 1 h, the mixture was cooled to room temperature and the phases which formed were separated. The lower phase is dried at 80 ° C and a pressure of 10 mbar. 7.0 g of butyl 3-methylimidazolium acetate were obtained.

Claims

claims

1. Process for the preparation of ionic liquids of the formula (I)

[A] ⁺ _n [Y] ⁿ - (I)

in which

n is 1, 2, 3 or 4; and

[Yf ^" for an anion selected from the group of sulfates, sulfites and sulfonates, the group of phosphates, the group of phosphonates and phosphinates, the group of phosphites, the group of phosphonites and phosphinites, the group of carboxylic acids, or

NO ₃ ^" ;

stand;

by adding an ionic liquid of the formula (II)

[A] ⁺ [X] - (II)

in which

[A] ^{+ has} the meaning given above; and

[X] ^" fluoride, chloride, bromide or iodide;

mean;

with an acid of formula IM

H ⁺ _n [Y] ⁿ - (III)

where n and [Y] "^{" have} the abovementioned meaning; reacted;

wherein, the forming acid of formula IV

H ⁺ [X] ^" (IV)

where [X] ^"has the meaning given above;

with an amine of the formula V

NR ¹ R ¹ R ³ (V)

in which

R ¹ , R ² and R ^{3 are} independently hydrogen or dC ₂ o-alkyl, which may be optionally substituted, wherein the number of carbon atoms of the radicals R ¹ , R ² and R ^{3 taken} together is at least 10;

mean;

intercepted;

and the resulting ammonium halide of formula VI

[HN R ¹ R ² R ³ J ⁺ [X] ^" (Vl)

wherein the radicals X, R, R and R have the abovementioned meaning;

is separated.

2. Process according to claim 1, wherein [A] ⁺ in the formulas I and II for [A] ⁺ are selected for a cation from the compounds of the formulas (Ia) to (Iv),

(Ia) (Ib) (Ic)

(Id) (Ie) (If)

(ig) (ig ¹ ) (Ih)

(Ik) (Ik ') (H)

(Im) (In) (In)

(Ip) (Iq) (Iq ')

(Iq ") (Ir) (Ir ')

(Ir ") (Is) (It)

R ^b R c I ^b ⁺ I a ⁺ a

R-P-R S-R

II ^RR

(Iu) (Iv)

stands, where

• The radicals R ^a to R 'are independently hydrogen or a carbon-containing organic, saturated or unsaturated, a-cyclic or cyclic, aliphatic, aromatic or araliphatic see, unsubstituted or by 1 to 5 heteroatoms or functional

Groups interrupted or substituted radical having 1 to 20 carbon atoms, wherein the radicals R ^a to R ', which are bonded in the abovementioned formulas (I) to a carbon atom (and not to a heteroatom), in addition to halogen or a functional group can stand;

or

two adjacent radicals from the series R ^a to R 'together also represent a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Residue with 1 to 30 carbon atoms.

Process according to claims 1 or 2, wherein [Y] ^{n "} in the formulas I and IM is selected from an anion

The group of sulfates, sulfites and sulfonates of the general formula: SO ₄ ^{2 "} , HSO ₄ ^" , SO ₃ ^{2 "} , HSO ₃ ^" , R ^{A #} OSO ₃ ^" , R ^{B #} SO ₃ ^" ; The group of phosphates of the general formula PO ₄ ^{3 "} , HPO ₄ ^2" , H ₂ PO ₄ ^" , R ³ PO ₄ ^2" , HR ^{A #} PO ₄ ^" , R ^{A #} R ^{B #} PO ₄ ^" ;

The group of phosphonates and phosphinates of the general formula: R ^{A #} HPO ₃ ^" , R ^{A #} R ^{B #} PO ₂ ^" , R ^{A #} R ^{B #} PO ₃ ^" , • the group of phosphites of the general formula:

PO ₃ ^{3 "} , HPO ₃ ^2" , H ₂ PO ₃ ^" , R ³ PO ₃ ^2" , R ^{A #} HPO ₃ ^" , R ^{A #} R ^{B #} PO ₃ ^" ;

The group of phosphonites and phosphinites of the general formula: R ^{A #} R ^{B #} PO ₂ ^" , R ^{A #} HPO ₂ ^" , R ^{A #} R ^{B #} PO ^" , R ^A HPO ^" ;

• the group of carboxylic acids of the general formula: R ^{A #} COO ^" ;

NO ₃ ^" ;

where R ^{A #} and R ^{B #} are each independently hydrogen, Ci-C ₃₀ - alkyl, optionally substituted by one or more nonadjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstitu- ierte imino ₂ - Ci ₈ alkyl, C ₆ -C ₄ aryl, C ₅ -C ₂ cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-comprising heterocycle, where two of them jointly aromatic an unsaturated, saturated or , which may optionally form a ring interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups, where the radicals mentioned are each additionally denoted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen , Heteroatoms and / or heterocycles may be substituted.

4. Process according to claims 1 to 3 wherein [X] ^" in the formulas II and IV are chloride or bromide.

5. Process according to claims 1 to 4, wherein [A] ^{+ represents} a cation selected from the group of the compounds Ia, Ie, If; Ig, Ig, Ih Ii, Ij, Ij ', Ik, Ik', II, Im, Im ', In or

In 'is.

6. Process according to claims 1 to 5, wherein [A] ^{+ is} a cation selected from the group of the compounds Ia, Ie or If.

7. Process according to claims 1 to 6 wherein [Y] ^{n "} in the formulas I and IM for an anion selected from the group SO ₄ ^2" HSO ₄ ^" , C _r C ₄ alkyl COO ^" , C _r C ₄ - Haloalkyl-COO ^" , C _r C ₄ -alkyl-SO ₃ ^" , or C _r C ₄ haloalkyl-SO ₃ ^" stands.

8. Process according to claims 1 to 7, characterized in that the separation of the ammonium halide of the formula VI from the ionic liquid of the formula I is carried out by liquid / liquid phase separation.

9. Process according to claims 1 to 8, characterized in that the amine of formula V is recovered from the separated ammonium halide of formula VI.

10. The method according to claim 9, characterized in that reacting the ammonium halide of the formula VI with a strong base and the amine of the formula V is separated.

1 1. A process according to claims 9 to 10, characterized in that the A- min of formula V is continuously fed to a mixture of ionic liquid of the formula II and acid of the formula III, the ammonium halide of the formula VI formed is continuously separated and from the ammonium halide recovered amine of formula V is fed to the reaction mixture again.

12. The method of claim 1 1, wherein both the amine of formula V and the mixture of ionic liquid of formula II and acid of the formula IM are continuously fed to a mixing and separating apparatus.