WO2007088152A1 - Process for preparing isocyanates - Google Patents

Abstract

A process for preparing isocyanates by reacting olefins with isocyanuric acid in a solvent, the solvent being an ionic liquid. The ionic liquid is preferably selected from (A) salts of the general formula (I) in which n is 1, 2, 3 or 4, [A]<SUP>+</SUP> is a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Y]<SUP>n-</SUP> is a mono-, di-, tri- or tetravalent anion; (B) mixed salts of the general formulae (II) [A1]<SUP>+</SUP>[A<SUP>2</SUP>]<SUP>+</SUP> [Y]<SUP>n-</SUP> (IIa), where n = 2; [A<SUP>1</SUP>]<SUP>+</SUP> [A<SUP>2</SUP>]<SUP>+</SUP>[A<SUP>3</SUP>]<SUP>+</SUP> [Y]<SUP>n-</SUP> (IIb), where n = 3; [A<SUP>1</SUP>]<SUP>+</SUP> [A<SUP>2</SUP>]<SUP>+</SUP>[A<SUP>3</SUP>]<SUP>+</SUP>[A<SUP>4</SUP>]<SUP>+</SUP> [Y]<SUP>n-</SUP> (IIc), where n = 4 and where [A<SUP>1</SUP>]<SUP>+</SUP>, [A<SUP>2</SUP>]<SUP>+</SUP>, [A<SUP>3</SUP>]<SUP>+</SUP> and [A<SUP>4</SUP>]<SUP>+</SUP> are each independently selected from the groups mentioned for [A]<SUP>+</SUP> and [Y]<SUP>n-</SUP> is as defined under (A).

Description

Process for the preparation of isocyanates

description

The invention relates to a process for the preparation of isocyanates by reacting olefins with isocyanic acid in a solvent.

Isocyanates are produced in large quantities and serve mainly as starting materials for the production of polyurethanes. They have hitherto been produced predominantly by reacting the corresponding amines with phosgene. The continuous production of organic isocyanates by reaction of primary organic amines with phosgene is widely described and is carried out on an industrial scale (see, eg, Ullmanns Enzyklopadie der Technischen Chemie, Volume 7 (Polyurethanes), 3rd revised edition, Carl Hanser Verlag, Munich - Vienna, pages 76 ff. (1993)).

Efforts have long been made to replace the current production process for isocyanates by reacting amines with phosgene with less expensive, less expensive and more environmentally friendly processes.

An alternative synthesis of isocyanates can be carried out without the use of phosgene by addition of isocyanic acid (HNCO) to olefins. The addition of HNCO to a C = C double bond was reported in F.W. Hoover, H.S. Rothrock, J. Org. Chem. 28 (1963), pages 2082 et seq., Et al. for the addition of HNCO to butyl vinyl ether to 1-butoxy-ethyl isocyanate. The reaction was carried out in the liquid phase at about room temperature. HNCO was obtained by the thermal decomposition of cyanuric acid. Specifically, the preparation of 1-butoxyethyl isocyanate by addition of butyl vinyl ether to a stirred mixture of benzene, isocyanic acid and catalytic amounts of p-toluenesulfonic acid and subsequent distillation of the resulting product. In another example, a mixture of vinyl butyl ether and isocyanic acid is added dropwise to a stirred mixture of diethyl ether and catalytic amounts of p-toluenesulfonic acid. Further examples relate to the preparation of 1-ethoxyethyl isocyanate, 1- (2-methacryloxyethoxy) ethyl isocyanate, 1- (2-methoxyethoxy) ethyl isocyanate, 1-phenoxyethyl isocyanate, 2-tetrahydropyranyl isocyanate, 1, 1 '- (ethylenedioxy) diethyl diisocyanate and 1-butoxy-1-methylethyl isocyanate, being carried out in ethyl ether or in benzene as a solvent.

FW Hoover and HS Rothrock, J. Org. Chem. 29 (1964), p. 143 ff., Describe the addition of HNCO to divinylbenzene, dicyclopentadiene, vinylacetylene, 1-methyl-3- methylene-1-phenylcyclobutane, 1-methylcyclohexene, 2,3-dimethyl-1,3-butadiene and p-methoxy-α-methylstyrene. In the examples, working is carried out in toluene as solvent and in the presence of ammonium tosylate and hydroquinone.

A disadvantage of this method is that only very reactive olefins can be reacted with activated double bond, and that HNCO must be isolated as a pure substance in liquid form.

The object of the invention is to provide an advantageous process for the preparation of isocyanates.

The object is achieved by a process for the preparation of isocyanates by reacting olefins with isocyanic acid in a solvent, characterized in that the solvent is an ionic liquid.

It has been found that HNCO is soluble in ionic liquids and stabilized. Thus, high HNCO concentrations can be provided in the liquid phase without trimerization of HNCO to cyanuric acid. Liquefaction of HNCO can be omitted. This is generally added in gaseous form. At higher temperatures, stabilization reduces the volatility of HNCO. Higher temperatures and / or HNCO concentrations, however, require higher reaction rates.

In the context of the present invention, ionic liquids are understood as meaning compounds which have at least one cationic center and at least one anionic center, in particular at least one cation and at least one anion, one of the ions, in particular the cation, being organic.

Ionic liquids are, according to the definition of Wasserscheid and Keim in: Angewandte Chemie 2000, 1 12, 3926-3945 at relatively low temperatures melting salts of non-molecular, ionic character. They are already liquid at relatively low temperatures and relatively low viscous. They have very good solubilities for a large number of organic, inorganic and polymeric substances. In addition, they are generally non-flammable, non-corrosive and have no measurable vapor pressure.

Ionic liquids are compounds that are formed from positive and negative ions, but are charge-neutral overall. The positive as well as the negative ions are predominantly monovalent, but it is also possible to use multivalent anions and / or cations, for example one to five, preferably one to four, more preferably with one to three and most preferably with one to two electrical charges per ion. The charges may be located at different localized or delocalized regions within a molecule, ie, betaine-like, or even distributed as a separate anion and cation. Preference is given to those ionic liquids which are composed of at least one cation and at least one anion.

The invention is not limited to special ionic liquids; It is possible to use all suitable ionic liquids, including mixtures of different ionic liquids.

Ionic liquids in the sense of the present invention are preferred

(A) Salts of the general formula (I)

[Ai; [Y] ⁿ - (I),

where n is 1, 2, 3 or 4, [A] ^{+ is} a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Y] ^{n 'is} a , di-, trivalent or tetravalent anion;

(B) mixed salts of the general formulas (II)

[A ¹ J ⁺ [A ² J ⁺ [Y] ⁿ - (IIa) where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ⁿ - (IIb), where n = 3; or

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ⁿ - (Mc), where n = 4 and

where [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ and [Y] ^{n "is} the meaning mentioned under (A) has.

Preferably, the ionic liquids have a melting point of less than 180 ° C. The melting point is particularly preferably in the range from -50 ° C. to 150 ° C., more preferably in the range from -20 ° C. to 120 ° C., and especially preferably below 100 ° C.

Compounds which are suitable for forming the cation [A] ⁺ of ionic liquids are known, for example, from DE 102 02 838 A1. Thus, such compounds may contain oxygen, phosphorus, sulfur or in particular nitrogen atoms, for example at least one nitrogen atom, preferably 1 to 10 nitrogen atoms, especially preferably 1 to 5, very particularly preferably 1 to 3 and in particular 1 to 2 nitrogen atoms. Optionally, other heteroatoms such as oxygen, sulfur or phosphorus atoms may be included. The nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquid from which, in equilibrium, a proton or an alkyl radical can then be transferred to the anion to produce an electrically neutral molecule.

In the event that the nitrogen atom is the carrier of the positive charge in the cation of the ionic liquid, in the synthesis of the ionic liquids, a cation can first be generated by quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle. The quaternization can be carried out by alkylation of the nitrogen atom. Depending on the alkylating reagent used, salts with different anions are obtained. In cases where it is not possible to form the desired anion during the quaternization, this can be done in a further synthesis step. Starting from, for example, an ammonium halide, the halide can be reacted with a Lewis acid to form a complex anion from halide and Lewis acid. Alternatively, replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt with precipitation of the metal halide formed, via a ion exchanger or by displacement of the halide ion by a strong acid (with liberation of the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 112, p. 3926-3945 and the literature cited therein.

Suitable alkyl radicals with which the nitrogen atom in the amines or nitrogen heterocycles can be quaternized, for example, are C 1 -C ₈ -alkyl, preferably C 1 -C 10 -alkyl, particularly preferably C 1 -C ₆ -alkyl and very particularly preferably methyl. The alkyl group may be unsubstituted or have one or more identical or different substituents.

Preference is given to those compounds which contain at least one five- to six-membered heterocycle, in particular a five-membered heterocycle, which has at least one nitrogen atom and, if appropriate, an oxygen or sulfur atom. Also particularly preferred are those compounds which contain at least one five- to six-membered heterocycle which has one, two or three nitrogen atoms and one sulfur atom or one oxygen atom, very particularly preferably those with two nitrogen atoms. Further preferred are aromatic heterocycles. Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol and in particular below 250 g / mol.

Furthermore, preference is given to those cations which are selected from the compounds of the formulas (IIIa) to (IIIw),

(purple) (MIb) (MIc)

(MId) (MIe) (MIf)

Cing) (mg ¹ ) (MIh)

(inj) (MIj ')

(Ulm) (MIm ') In)

(Mn) (MIo)

(MIp) (MIq) (MIq ')

(MIq ") (Mir) (MIr ')

(MIr ") (MIs) (With)

(MIu) Iv) (MIw)

and oligomers containing these structures.

Further suitable cations are compounds of the general formula (IMx) and (MIy) R ² R ²

₃ 1 -H ₁ I +.,

R-P-R S-R

I i

R R

(MIx) (MIy)

and oligomers containing this structure.

In the above formulas (MIa) to (MIy) stand

• 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 ¹ to R ⁹ independently of one another are hydrogen, a sulfo group 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 having 1 to 20 carbon atoms, where the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) 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 ¹ to R ⁹ together, also for a dihydric, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups substituted radical having 1 to 30 carbon atoms.

Suitable hetero atoms in the definition of the radicals R and R ¹ to R ^{9 are in} principle all heteroatoms in question which are capable of formally a -CH ₂ -, a -CH =, a -C≡ or a = C = group to replace. When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. As preferred groups, in particular -O-, -S-, -SO-, -SO ₂ -, -NR'-, -N =, -PR'-, - PR ' ₂ and -SiR' ₂ - may be mentioned, wherein it the radicals R 'are the remainder of the carbon-containing radical. The radicals R ¹ to R ⁹ can in the cases in which these in the above formulas (IM) to a carbon atom (and not bound to a heteroatom) may 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 carbonyl group), -NH ₂ (amino), = NH (imino), -COOH (carboxy), -CONH ₂ (carboxamide), -SO ₃ H (sulfo ) and -CN (cyano). Functional groups and heteroatoms can 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-C ₄ alkyl) amino, CrC ₄ - alkyloxycarbonyl or dC ₄ alkyloxy.

Halogens are fluorine, chlorine, bromine and iodine.

The radical R preferably stands for

• straight-chain or branched, unsubstituted or C 1 -C ₈ -alkyl which has been monosubstituted to hydroxyl, halogen, phenyl, cyano, C ₁ -C ₆ -alkoxycarbonyl and / or SO ₃ H and has a total of 1 to 20 carbon atoms, such as, for example, methyl, ethyl , 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 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- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, trifluoromethyl, difluoromethyl,

Fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, 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 -C 6 -alkyl as an 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 O) _m -CH ₂ CH ₂ CH ₂ CH ₂ O- with R ^A and R ^B preferably hydrogen, methyl or ethyl and m preferably 0 to 3, in particular 3-oxabutyl . 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9, 12-tetraoxatetradecyl;

• vinyl; and

• N, N-di-d-Ce-alkyl-amino, such as N, N-dimethylamino and N ₁ N-diethylamino.

Particularly preferably, the radical R is unbranched and unsubstituted C ₁ -C 1 represents ₁ 8 alkyl, such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, -Decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, in particular methyl, ethyl, 1-butyl and 1-octyl, and also CH ₃ O- (CH ₂ CH ₂ O) _n -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _n -CH ₂ CH ₂ - with m equal to 0 to 3.

The radicals R ¹ to R ⁹ 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 Ci ₈ 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 C ₂ -Ciβ alkenyl; Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C ₆ -C ₂ -aryl;

• optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted _C5-Ci2 cycloalkyl;

• where appropriate by functional groups, aryl, alkyl, aryloxy, alkyloxy, halo-, heteroatoms and / or heterocycles substituted _C5-Ci2 cycloalkenyl; 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 containing 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, Substance 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 substituted d-C-iβ-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, cycloh exylmethyl, 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-aminoethyl, 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-Ph enoxypropyl, 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) H 2a + b with m being 1 to 30, 0 <a <im 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 F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ ), chloromethyl, 2-chloroethyl, trichloromethyl, 1, 1-dimethyl 2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n Butoxythiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa-octyl, 1 1-hydroxy-3,6,9 trioxa undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl , 14-hydroxy-5,10-dioxa-tetradecyl,

5-Methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1 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-tιϊoxa-undecyl, 7-ethoxy-4-oxo-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.

C ₂ 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 groups -C ₈ -alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F 2 (ma) - (ib) H 2a-b with im <30, 0 <a <m and b = 0 or 1.

C 1 -C ₂ -aryl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably phenyl, toIyI, xylyl, .alpha.-naphthyl, .beta.-naphthyl, 4 -Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, / so-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 C ₆ F _(S-3) H ₃ with 0 <a <5.

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₅ -C ₂ -cycloalkyl is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthio cyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F ₂ ( _m -a) - (ib) H _{2 3} -b with m <30, 0 <a <m and b = 0 or 1 and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

In optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₅ -C ₂ is cycloalkenyl, it is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5- Cyclohexadienyl or C _n F ₂ (ma) -3 (ib) H _{2 3} -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-containing heterocycle are 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 -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.

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.

Particularly preferably, the radicals R ¹ to R ⁹ are each independently

• hydrogen;

• linear or branched, unsubstituted or mono- or polysubstituted by hydroxy, halogen, phenyl, cyano, Cr C ₆ alkoxycarbonyl and / or SO ₃ H-substituted C-ι-C ₈ alkyl with a total of 1 to 20 carbon atoms, such as methyl, Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 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- (Ethoxycarbonyl) -ethyl, 2- (n-butoxy-carbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, 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 6 alkyl as end group, such as R ^A O- (CHR ^B -CH ₂ -O) _m -CHR ^B -CH ₂ - or

R 1 is - (CH ₂ CH ₂ CH ₂ CH ₂ O) _n -CH ₂ CH ₂ CH ₂ CH ₂ O- with R ^A and R ^{B is} preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9, 12-tetraoxatetradecyl;

• vinyl; and

• N ₁ N-di-Cr to Cβ-alkyl-amino, such as N, N-dimethylamino and N ₁ N-diethylamino.

Most preferably, the radicals R ¹ to R ⁹ independently of one another are hydrogen or C 1 -C ₈ -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 CH ₃ O- (CH ₂ CH ₂ O) _m - CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _n -CH ₂ CH ₂ - with m is 0 to third

Very particular preference is given to pyridinium ions (IIIa) which are those in which • one of the radicals R ¹ to R ^{5 is} methyl, ethyl or chlorine and the remaining radicals R ¹ to R ^{5 are} hydrogen;

• R ^{3 is} dimethylamino and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen;

• all radicals R ¹ to R ^{5 are} hydrogen; • R ^{2 is} carboxy or carboxamide and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen; or

• R ¹ and R ² or R ² and R ^{3 are} 1, 4-buta-1, 3-dienylene and the remaining R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen;

and in particular those in which

• R ¹ to R ^{5 are} hydrogen; or

• one of the radicals R ¹ to R ^{5 is} methyl or ethyl and the remaining radicals R ¹ to R ^{5 are} hydrogen. Particularly preferred pyridinium ions (IIIa) which may be mentioned 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- (1-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-ethylpyridinium, 1, 5-diethyl-2-methyl- pyridinium, 1- (1-butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium and 1- (1-octyl) -2-m ethyl 3-ethylpyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethylpyridinium and 1- (1-hexadecyl ) -2-methyl-3-ethyl-pyridinium.

Very particular preference is given to those pyridazinium (IMb), in which

• R ¹ to R ^{4 are} hydrogen; or

• one of the radicals R ¹ to R ^{4 is} methyl or ethyl and the remaining radicals R ¹ to R ^{4 are} hydrogen

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

• R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl; or R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen.

Very particular preference is given as Pyraziniumionen (IMd) such a, in which

• R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl;

• R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen;

• R ¹ to R ^{4 are} methyl; or

• R ¹ to R ^{4 are} methyl hydrogen.

Very particularly preferred as Imidazoliumionen (Never) are those in which

• R ^{1 is} hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R ² to R ^{4 are} independently hydrogen, methyl or ethyl , Very particularly preferred imidazolium ions (MIe) which may be mentioned are 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) -3-octylimidazolium, 1- (1-tetradecyl) -S-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, 1,4-trimethylimidazolium, 1,4-dimethylmethyl 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.

Very particular preference is given to pyrazolium ions (Nif), (IMg) or (MIg ') those in which

• R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl.

Very particular preference is given as Pyrazoliumionen (IMh) such, in which

Are • R ¹ to R ⁴ are independently hydrogen or methyl.

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

• independently of one another R ¹ to R ^{6 are} hydrogen or methyl.

Very particularly preferably used as 2-pyrazolinium (MIj) or (MIj ') are those in which • R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to using as 3-pyrazolinium ions (MIk) or (MIk ') those in which • R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ³ to R ^{6 are} independently hydrogen or methyl.

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

• R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R ³ and R ^{4 are} independently hydrogen, methyl or ethyl, and R ⁵ and R ^{6 are} independently hydrogen or methyl.

Very particularly preferred as Imidazoliniumionen (Ulm) or (MIm ') are those in which

• R ¹ and R ^{2 are} independently hydrogen, methyl or ethyl and R ³ to R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to imidazolinium ions (MIn) or (MIn ') those in which

• R ¹ to R ^{3 are} independently hydrogen, methyl or ethyl and R ⁴ to R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to using as thiazolium ions (MIo) or (IMo ') and as oxazolium ions (MIp) those in which

• R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² and R ^{3 are} independently hydrogen or methyl.

Very particular preference is given to using as 1, 2,4-triazolium ions (IMq), (IMq ') or (MIq ") those in which

• R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ^{3 is} hydrogen, methyl or phenyl.

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

• R ^{1 is} hydrogen, methyl or ethyl and R ² and R ^{3 are} independently hydrogen or methyl, or R ² and R ³ together are 1, 4-buta-1, 3-dienylene.

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

• R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{9 are} independently hydrogen or methyl. With very particular preference one uses as imidazolidinium ions (mit) those in which

• R ¹ and R ^{4 are} independently hydrogen, methyl, ethyl or phenyl and R ² and R ³ and R ⁵ to R ^{8 are} independently hydrogen or methyl.

Very particular preference is given as ammonium ions (MIu) such, in which

• R ¹ to R ^{3 are} independently of each other Ci-Ci ₈ alkyl; or

• R ¹ and R ² together ^are 1, 5-pentylene or 3-oxa-1, 5-pentylene, and R ³ is C ₁ -C ₁ 8 alkyl, 2-hydroxyethyl or 2-cyanoethyl.

As very particularly preferred ammonium ions (MIu) may be mentioned methyl tri (1-butyl) -ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.

Examples of the tertiary amines from which the quaternary ammonium ions of the general formula (IMu) are derived by quaternization with the abovementioned radicals R are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethylhexylamine, Diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2-ethyl - hexyl) amine, di-isopropylethylamine, di-iso-propyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, di-iso-propyl (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, Nn-butylpyrrolidine, N-sec-Butylpyrrodidin, N-tert-butylpyrrolidine, Nn-Pentylpyrrolidin, N ₁ N- dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-di-n-butylcyclohexylamine, N-n-propylpiperidine, N-isopropylpiperidine, Nn-butylpiperi din, N-sec-butylpiperidine, N-tert-butylpiperidine, Nn-pentylpiperidine, Nn-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, Nn-pentylmorpholine, N-benzyl-N-ethylaniline, N-benzyl Nn-propylaniline, N-benzyl-N-isopropylaniline, N-benzyl-Nn-butylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di- n-butyl-p-toluidine, diethylbenzylamine, di-n-propylbenzylamine, di-n-butylbenzylamine, diethylphenylamine, di-n-propylphenylamine and di-n-butylphenylamine.

Preferred tertiary amines (MIu) are di-iso-propylethylamine, diethyl-tert-butylamine, diisopropyl-propylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.

Particularly preferred tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers. Another preferred tertiary amine having three identical residues is triallylamine. Very particularly preferred as guanidinium ions (MIv) are those in which

• R ¹ to R ⁵ are methyl.

As a very particularly preferred guanidinium ion (MIv) may be mentioned N, N, N ', N', N ", N" - hexamethylguanidinium.

Very particularly preferred as cholinium ions (MIw) are those in which

• R ¹ and R ^{2 are} independently methyl, ethyl, 1-butyl or 1-octyl and R ^{3 is} hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ;

• R ^{1 is} methyl, ethyl, 1-butyl or 1-octyl, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁴ group and R ³ and R ^{4 are} independently hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ; or

• R ^{1 is} a -CH ₂ -CH ₂ -OR ⁴ group, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁵ group and R ³ to R ^{5 are} independently hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or

-PO (OH) ₂ are.

Particularly preferred cholinium ions (MIw) are those in which R ^{3 is} selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 1 1-methoxy 3,6,9-trioxa undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy 5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-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.

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

R ¹ to R ^{3 are,} independently of one another, C 1 -C ₈ -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.

Among the above-mentioned heterocyclic cations, the pyridinium ions, pyrazolinium, pyrazolium ions and imidazolinium and imidazolium ions are preferable. Furthermore, ammonium ions are preferred.

Particular preference is given to 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-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-methyl-pyridinium, 1- (1-butyl) -2-methyl-3-ethyl-pyridinium, 1- (1-hexyl) -2-methyl-3-ethyl pyridinium, 1- (1-octyl) -2-methyl-3-ethyl-pyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetra-decyl) -2- Methyl 3-ethyl-pyridinium, 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium, 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-0ctyl 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-Tetra decyl) -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.

In a particular embodiment of the invention, the solvent used is an ionic liquid mixed with hydrogen halide, in particular hydrogen chloride. The ratio of hydrogen chloride to ionic liquid in this embodiment is greater than 0 to 400 mol%, preferably 5 to 300 mol%, very particularly preferably 10 to 150 mol%, based on the ionic liquid. Instead of hydrogen halide, it is generally possible to use acids (protic, aprotic, Lewis acids and also solid acids, for example zeolites), preferably in the amounts indicated above.

As anions, in principle, all anions can be used.

Preferred anions [Y] ^{n "} are selected from the group of the halides and halogen-containing compounds, the sulfates, sulfites and sulfonates, the phosphates, phosphonates, phosphinates, phosphites, phosphonites and phosphinites, the carboxylates, the borates and boronates, the Silicates, the carboxylic acid imides, bis (sulfonyl) imides and sulfonylimides and the methides.

It is believed that by addition of contained in the ionic liquid

Anions [Y] ^" on the one hand and in the cation [A] ⁺ bound protons (or in general of R ^Θ groups) on the other hand on the HNCO molecules these in the ionic liquid be stabilized. Thus, HNCO is presumably stabilized as carbamoyl chloride in the presence of hydrogen chloride chemically bound in the ionic liquid and / or additionally added. Accordingly, other anions, such as the halides listed below and halogen-containing anions act.

For example, the anion [Yf ^" is selected from

The group of halides and halogen-containing compounds of the formula:

F, Cr, Br ^", r, BF ^_4", PF ₆ ^", CF ₃ SO ^_3", (CF ₃ SO _{3) 2} N-, CF ₃ CO ₂ ^", CCl ₃ CO ^_2", CN ^{", SCN"} , OCN ^"

The group of sulfates, sulfites and sulfonates of the general formula: SO ₄ ^{2 "} , HSO ₄ ^" , SO ₃ ^{2 "} , HSO ₃ ^" , ROSO ₃ ^" , R ³ 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 ³ PO ₄ ^" , R ³ R ^b PO ₄ ^" • the group of phosphonates and Phosphinates of the general formula: R ³ H PO ₃ ^" , R ³ R ^b PO ₂ ^" , R ³ 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 ³ HPO ₃ ^" , R ³ R ^b PO ₃ ^"

The group of phosphonites and phosphinites of the general formula: R ³ R ^b PO ₂ ^" , R ³ HPO ₂ ^" , R ³ R ^b P 0 ^" , R ³ HPO ^"

The group of carboxylic acids of the general formula: R ³ COO ^"

The group of borates of the general formula:

BO ₃ ^{3 "} , HBO ₃ ^2" , H ₂ BO ₃ ^" , R ³ R ^b BO ₃ ^" , R ³ HBO ₃ ^" , R ³ BO ₃ ^2" , B (0R ³ ) (0R ^b ) (0R ^c ) (0R ^d ) ^" , B (HSO ₄ ) ^" , B (R ³ SO ₄ ) ^"

The group of boronates of the general formula: R ³ BO ₂ ^{2 "} , R ³ R ^b B0 ^"

The group of silicates and silicic acid esters of the general formula: SiO ₄ ^{4 "} , HSiO ₄ ^3" , H ₂ SiO ₄ ^{2 "} , H ₃ SiO ₄ ^" , R ³ SiO ₄ ^{3 "} , R ³ R ^b Si0 ₄ ^2" , R ³ R ^b R ^c Si0 ₄ ^" , HR ³ SiO ₄ ^2" , H ₂ R ³ SiO ₄ ^" , HR ³ R ^b Si0 ₄ ^"

The group of the alkyl or aryl silane salts of the general formula: R ³ SiO ₃ ^{3 "} , R ³ R ^b Si0 ₂ ^2" , R ³ R ^b R ^c Si0 ^" , R ³ R ^b R ^c SiO ₃ ^" , R ³ R ^b R ^c Si0 ₂ ^" , R ³ R ^b Si0 ₃ ^2"

The group of the carboxylic imides, bis (sulfonyl) imides and sulfonyl imides of the general formula:

der Gruppe der Methide der allgemeinen Formel:

the group of methides of the general formula:

SO 2 ₉ - ~ R ³

R ^b -O ₂ S SO ₂ -R ^C

In this formula, R ^a , R ^b , R ^c and R ^d are each independently hydrogen, C ₁ -C 30 -alkyl, optionally substituted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imines. n groups interrupted C ₂ -C ₈ alkyl, C ₆ -C ₄ -ArVl, C ₅ -C ₂ -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, wherein two of them together unsubstituted, saturated or aromatic, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups ring, said radicals each additionally by functional groups, aryl, alkyl, aryloxy, alkyloxy, Halogen, heteroatoms and / or heterocycles can be substituted.

Therein, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, substituted CrCiβ-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, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 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, 2-methoxycarbonethyl, 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-octyloxyethyl, chloromethyl, trichloromethyl, trifluoromethyl, 1 , 1-Dimethyl-2-chloroethyl, 2-methoxy-isopropyl, 2-ethoxyethyl, 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-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 or 6-ethoxyhexyl.

Optionally C ₂ -C ₈ -alkyl which is interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups are, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3, 6-dioxaoctyl, 1 1-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 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-dioxo-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-dioxo-octyl, 1-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxaheptyl, 1-ethoxy-4,8- dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 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 building block 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-dC 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 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 is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

Optionally by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen,

Heteroatoms and / or heterocycles substituted C ₆ -C ₄ -aryl are, for example

Phenyl, ToIyI, XyIyI, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethyl phenyl, diethylphenyl, isopropylphenyl, 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 ethoxymethylphenyl.

Me optionally substituted by functional groups, aryl, alkyl, aryloxy, halogen, Heteroato- and / or heterocycles substituted _C5-Ci2 cycloalkyl, 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, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxifuryl , Dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.

Preferred anions are selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates.

Particularly preferred anions are fluoride, chloride, bromide, iodide, SCN ^" , OCN ^" , CN ^" , acetate, C _r C ₄ -alkyl sulfates, R ^a -COO ^" , R ³ SO ₃ ^" , R ^a R ^b PO ₄ ^" , Methanesulfonate (CH ₃ SO ₃ ^" ), tosylate, C _r C ₄ dialkyl phosphates, (C ₂ H ₅ O) ₂ PO ^" , hydrogen sulfate, triflate (CF ₃ SO ₃ ^" ), AICI ₄ ^" , Al ₂ Cl ₇ ^" .

In the process according to the invention, an ionic liquid of the formula I is used or a mixture of ionic liquids of the formula I, preferably an ionic liquid of the formula I is used.

According to another embodiment of the invention, it is possible to use an ionic liquid of the formula II or a mixture of ionic liquids of the formula II.

According to another embodiment of the invention, it is possible to use a mixture of ionic liquids of the formulas I and II. Preferably, an ionic liquid of the formula I is used.

Specific examples of suitable ionic liquids are ethylmethylimidazolium chloride, preferably with hydrogen chloride, in particular with one mole of HCl, methylimidazolium butanesulfonic acid triflate and pyridinium-3-S-triflate hydrogen sulfate.

In a particular embodiment of the invention, the solvent used is an ionic liquid mixed with hydrogen halide, in particular hydrogen chloride. The ratio of hydrogen chloride to ionic liquid in this embodiment is greater than 0 to 400 mol%, preferably 5 to 300 mol%, very particularly preferably 10 to 150 mol%, based on the ionic liquid.

The process according to the invention can be used to prepare the customary industrially produced isocyanates. In general, these are - optionally substituted - straight-chain or branched aliphatic, cycloaliphatic or araliphatic mono-, di- or polyolefins having 2 to 100 carbon atoms. In particular, it is possible to react by the process according to the invention:

Straight-chain or branched C ₂ -C ₃₀ -OI ef ine to the corresponding alkyl isocyanates, for example propene to isopropyl isocyanate.

Substituted straight-chain or branched C ₂ -C ₃₀ -OI efine to the corresponding substituted alkyl isocyanates, for example chloroethene to 2-chloroethyl isocyanate. Straight-chained and branched alpha, omega-diolefins having 4 to 30 C atoms to the corresponding alkylene diisocyanates, for example 1, 5-hexadiene to hexamethylene diisocyanate. Another example of preferred alpha, omega-diolefins is 1,1-dodecene.

• Cyclic olefins and diolefins having 5 to 30 carbon atoms to the corresponding cycloalkyl isocyanates or cycloalkylene diisocyanates. Examples are the reaction of cyclohexene to give 1-cyclohexyl isocyanate, 1,3- or 1,4-cyclohexadiene to give 1,3- or 1,4-bisisocyanatocyclohexane, bis (methylidene) cyclohexane to bisisocyanatomethylcyclohexane, bis (cyclohexenyl) methane to methylenedicyclohexyl diisocyanate, from tricyclodecadiene to tricyclodecanediisocyanate and from bis (methylidene) tricyclodecane

Bis (isocyanatomethyl) tricyclodecane.

Alkenylbenzenes having 8 to 100 carbon atoms to the corresponding araliphatic isocyanates, for example of di (prop-1-enyl) benzene to (prop-1-enyl) phenylpropyl isocyanate (with one equivalent of HNCO) or to Bis (1- isocyanato-1-methylethyl) benzene (with 2 equivalents of HNCO). Another example of preferred alkenylbenzenes is alpha-methylstyrene.

To carry out the process according to the invention, the isocyanic acid is dissolved in the ionic liquid used as solvent and olefin is reacted with this solution.

In a preferred embodiment, the olefin is dispersed in the ionic liquid, the two-phase mixture of olefin and ionic liquid introduced and gaseous isocyanic acid, preferably in an inert gas stream such as a stream of nitrogen or argon, introduced into the mixture. The reaction can be carried out here preferably at low pressure. As reactors, for example, gassed stirred tanks or bubble column reactors can be used.

Alternatively, a 2-phase mixture of olefin and ionic liquid on the one hand and a solution of isocyanic acid in the ionic liquid on the other hand can be prepared and then mixed mixture and solution.

Furthermore, the ionic liquid can be preloaded with HNCO and the pure olefin added. The olefin may also be dissolved in a solvent dissolved in the ionic liquid.

The present invention also relates to the ionic liquids used according to the invention, which contain HNCO dissolved. The stabilized HNCO contained therein can also be provided in this way for other types of reactions, for example for substitution reactions. For example, HNCO may be present at least partially in the form of carbamoyl chloride in the ionic liquid.

The temperature range which is advantageous for the process according to the invention depends inter alia on the type and amount of the solvent and on the product to be produced

Isocyanate from. In general, the temperature in the reactor is between 10 ° C and

360 ° C and preferably between 40 ° C and 210 ° C and more preferably between

80 ° C and 150 ° C. Furthermore, the absolute pressure is generally between 0.2 bar and

50 bar, preferably between 0.8 bar and 25 bar, more preferably between 1 and 17 bar.

After the reaction, the mixture of substances, preferably by means of simple phase separation, optionally by adding a further solvent, in isocyanate, optionally with further solvent on the one hand and ionic liquid on the other hand, separated. Isocyanate remaining in the ionic liquid may, if necessary, be separated by means of additional extraction or crystallization of the ionic liquid. The isocyanate can be freed from by-products by the common purification methods.

The separated ionic liquid can then be recycled again as a solvent.

The isocyanic acid is preferably obtained by oxidation of HCN with oxygen in accordance with U.S. Pat. 4,364,913 and U.S. Pat. 4,389,386 on a catalyst, for example an Ag-Pd catalyst. Alternatively, HNCO can be generated by urea pyrolysis, with ammonia as a by-product. The latter can be separated from HNCO, for example as described in EP-A 0416236, if this proves to be necessary. It is also possible to produce HNCO by pyrolysis of cyanuric acid, the cyclic trimer of HNCO, preferably in the transport gas stream from an inert gas (generally nitrogen or argon). Cyanuric acid pyrolysis generally takes place at temperatures of 250 to 600 ° C.

The invention is further illustrated by the following example.

example

In a laboratory plant comprising a dosing device for cyanuric acid, a sublimator and a decomposer, HNCO was generated by thermal decomposition of cyanuric acid at about 400 ° C. Nitrogen was used as transport gas. Thus, a HNCO / N ₂ stream was provided containing approximately 40 g / h of HNCO in approximately 200 Nl / h of nitrogen. The HNCO / N ₂ stream was passed for about 20 minutes into a wash bottle containing 20 g of α-methylstyrene in 50 g of ethylmethylimidazolium chloride / HCl (1 mole of HCl per mole of ethylmethylimidazolium chloride) at 85 ° C. In the upper (lighter) product phase, the corresponding isocyanate (2-phenylpropyl isocyanate) was found. In addition, 2-phenyl-2-chloropropane was found as a by-product.

Claims

claims A process for the preparation of isocyanates by reacting olefins with isocyanic acid in a solvent, characterized in that the solvent is an ionic liquid. 2. The method according to claim 1, characterized in that the ionic liquid is selected from (A) Salts of General Formula (I) [Ai; [Y] ⁿ - (I) wherein n is 1, 2, 3 or 4, [A] ^{+ is} a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Yf ^"stands for a mono-, di-, tri- or tetravalent anion; (B) mixed salts of the general formulas (II) [A ¹ J ⁺ [A ² J ⁺ [Y] ⁿ - (IIa) where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ⁿ - (IIb), where n = 3; or [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ⁿ - (Mc), where n = 4 and where [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ and [Y] ^{n "is} the meaning mentioned under (A) has. 3. The method according to claim 2, characterized in that the cations [A] ⁺ , [A ¹ J ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ or [A ⁴ J ^{+ are} each selected from the group consisting of Pyridinium ions, pyridazinium ions, pyrimidinium ions, pyrazinium ions, imidazolinium ions, pyrazolium ions, 1-pyrazolinium ions, 2-pyrazolinium ions, 3-pyrazolinium ions, imidazolinium ions, thiazolium ions, Oxazolium ions, 1, 2,4-triazolium ions, 1, 2,3-triazolium ions, pyrrolidinium ions, imidazolidinium ions, ammonium ions, guanidinium ions, cholinium ions, phosphonium ions and sulfonium ions. 4. The method according to claim 3, characterized in that the cations [A] ⁺ , [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ or [A ⁴ ] ^{+ are} selected from the group consisting of pyridinium ions , Pyrazolinium ions, pyrazolium ions, imidazolinium ions, imidazolium ions and ammonium ions. 5. The method according to claim 3 or 4, characterized in that the cations [A] ⁺ , [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ or [A ⁴ ] ^{+ are} selected from the group consisting from 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1 -0ctyl) - pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-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-methyl-pyridinium, 1- (1-butyl) -2-methyl-3-ethyl-pyridinium, 1 - (1 -Hexyl) -2-methyl-3-ethyl-pyridinium, 1- (1-octyl) -2-methyl-3-ethyl-pyridinium, 1- (1-dodecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-Tetra-decyl) -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-dimethyl-imidazolium 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. 6. The method according to any one of claims 1 to 5, characterized in that the anion [Y] ^{n "is} selected from the group of halides and halogen-containing compounds, sulfates, sulfites and sulfonates, phosphates, phosphonates, phosphinates, phosphites, phosphonites and phosphinites, the carboxylates, the borates and boranates, the silicates, the carboxylic imides, bis (sulfonyl) imides and Sulfonylimides and the methides. 7. The method according to any one of claims 1 to 6, characterized in that the anion [Y] ^{n "} selected from the group of halides and halogen-containing Compounds, the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates. 8. The method according to any one of claims 1 to 7, characterized in that the anion [Y] ^{n "} selected from the group consisting of fluoride, chloride, bromide, iodide, SCN ^" , OCN ^" , CN ^" , acetate, C _r C _4- alkyl sulfates, R ^a -COO ^" , R ³ SO ₃ ^" , R ₃ RbPO ₄ , Methanesulfonate, tosylate, dC ₄ dialkyl phosphates, hydrogen sulfate, (C ₂ H ₅ O) ₂ PO ^" , Triflate, AICI ₄ ^" , AI ₂ CI ₇ ^" . 9. The method according to any one of claims 1 to 8, characterized in that the ionic liquid is used in admixture with an acid as a solvent. 10. The method according to claim 9, characterized in that the ionic liquid is used with 10 to 150 mol% of hydrogen halide, based on the ionic liquid. 1 1. A method according to any one of claims 1 to 10, characterized in that the olefin is dispersed in the ionic liquid, initially charged and gaseous iso-cyanic acid, optionally in an inert gas stream, is introduced into the dispersion. 12. The method according to any one of claims 1 to 10, characterized in that HNCO dissolved in the ionic liquid and the olefin is reacted with this solution. 13. The method according to any one of claims 1 1 or 12, characterized in that the olefin is used dissolved in a solvent. 14. Ionic liquids as defined in any one of claims 1 to 10, containing HNCO in dissolved form. 15. Ionic liquids according to claim 14, characterized in that HNCO is at least partially present as carbamoyl chloride.