EP2131955A1

EP2131955A1 - Dmc catalysts, method for the production thereof and use thereof

Info

Publication number: EP2131955A1
Application number: EP08708503A
Authority: EP
Inventors: Michael Triller; Matthias Schopohl; Veit Stegmann; Thomas Ostrowski
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2007-02-05
Filing date: 2008-01-31
Publication date: 2009-12-16
Also published as: US20100029961A1; US8354356B2; CN101646492A; WO2008095853A1; KR20090108118A; JP2010517742A; JP5254254B2; MX2009008311A; CN101646492B

Abstract

The invention relates to a method for producing DMC catalysts by reacting cyanometallate compounds with metal salts, characterized in that the reaction is performed in ionic fluids as the solvent.

Description

DMC CATALYSTS, PROCESS FOR THEIR PREPARATION AND USE THEREOF

The invention relates to a process for the preparation of DMC catalysts.

Multimetal cyanide compounds, often referred to as DMC catalysts, have long been known and widely described in the literature, for example, in US 3,278,457 and in US 5,783,513.

Such compounds are preferably used as catalysts for the preparation of polyether alcohols by addition of alkylene oxides to H-functional starter substances. These methods are also known.

The preparation of the DMC catalysts is usually carried out by the aqueous solution of a metal salt with the aqueous solution of a Cyanometallatε, often in the presence of at least one organic ligand, is reacted. The multimetal cyanide compound thus obtained is separated, washed and dried.

Water is a catalyst poison and must be removed as completely as possible in the DMC catalysts prepared as described in elaborate drying steps. Due to the requirement of complete water separation, the production process becomes complicated and expensive.

To remedy this deficiency, the preparation of the DMC catalysts can be carried out in a nonaqueous medium.

Thus, JP 2003 103177 describes the preparation of DMC catalysts in anhydrous organic solvents, such as alcohols, ethers, amides, nitriles, ketones, aldehydes or sulfides of metal halides (ZnXΣ) and a cyanometalate. The aim is to produce anhydrous DMC catalysts which have a higher and, above all, not with the inevitable results in conventional production residual water content fluctuating activity. The DMC catalysts thus prepared are used for the addition of alkylene oxides having at least three carbon atoms to H-functional starter substances.

No. 6,429,166 describes the preparation of DMC catalysts from a transition metal salt and a hexacyanometallic acid in low-boiling organic solvents. After precipitation of the DMC in the organic solvent, the resulting suspension is combined with a starter alcohol and then the organic solvent is removed, preferably by distillation. A disadvantage of this process is in particular that the distillation is energy-intensive and requires high safety technology because of the risk of exposure and fire. Furthermore, the DMC catalyst is not isolated, but it is always present as a relatively dilute suspension. This makes a production necessary where the catalyst should also be used, because the transport of the diluted catalyst suspensions is associated with increased costs and increased safety expenditure. In addition, a catalyst suspension can not be readily stored without the catalyst settling. Then the catalyst suspension would have to be stirred before use, whereby it can not be guaranteed that the sediment can be suspended completely homogeneously or can even be stirred.

No. 6,869,905 B1 describes the preparation of DMC catalysts from two transition-metal salts, none of which is a complex cyanometalate, and alkali cyanide in non-aqueous solution. Either polar-protic solvents such as alcohols or carboxylic acids or polar aprotic solvents such as ketones, nitriles, formamides or sulfoxides are used. The use of alkali metal cyanides also requires increased safety expenses.

WO 2006/117364 describes the preparation of DMC catalysts by reacting cyanometallic acid with a metal salt MR _W or MR _W Y _V , where R stands for the anion of a very weak acid (pKa value> = 20) and w is at least 1. This separates all commonly used zinc salts such. As zinc chloride, zinc oxide or zinc carboxylates as starting materials. The metal salts used are mostly zinc salts, such as diethylzinc. The use of the DMC catalysts thus prepared is preferably carried out for the reaction of H-functional starters, in particular monofunctional alcohols, with alkylene oxides.

Another problem in the production of polyether alcohols using DMC catalysts is that the addition of pure ethylene oxide is extremely difficult and often does not result in useful products. Since polyether alcohols are required with end blocks of pure ethylene oxide for many applications in the production of polyurethanes, there is a need to produce such products by means of DMC catalysts.

WO 2004/105944 describes a process for the preparation of DMC catalyst by precipitation from an emulsion. The precipitation emulsion consists of aqueous metal salt solution (preferably zinc chloride) and aqueous hexacyanocobaltic acid solution in a water-insoluble solvent, for example hydrocarbons or higher alcohols. When using these catalysts, the addition of ethylene oxide should be possible at the chain end.

A disadvantage of this preparation of the DMC catalysts is the long reaction time of about 20 hours without workup. In addition, there are the necessary enormous reaction volumes, which are necessary for a precipitation of microemulsions. Compared to a conventional DMC synthesis, the preparation of a microemulsion one further process step. The precipitation from an emulsion also requires the use of organic solvents both for the production and for breaking the emulsion as well as an increased effort in safety technology and waste disposal.

It was the object of the present invention to develop a process for the preparation of DMC catalysts, in which no water must be used, which is simple to carry out and manages without additional process steps and arise in the DMC catalysts, which have a high catalytic activity , Furthermore, when using these catalysts in the preparation of polyether alcohols, the addition of ethylene oxide should also be possible.

Surprisingly, the problem could be solved by the use of ionic liquids as solvents or suspending agents in the preparation of the DMC catalysts.

In Clavel et al., "Synthesis of Cyano-Bridged Magnetic Nanoparticles Using Room-Temperature Lonic Liquids", Chem. Eur. J. 2006, 12, 3798-3803, a method for the preparation of magnetic nanomaterials described in colloidal suspensions A metal salt was reacted with a cyanometalate salt in an ionic liquid containing tetrafluoroborate as an anion, but tetrafluoroborate-containing compounds are less suitable for multimetal cyanide compounds used as catalysts for the addition of alkylene oxides In the case of the use of the multimetal cyanide compounds as catalysts for the addition of alkylene oxides, such colloidal suspensions of multimetal cyanide compounds in ionic liquids are therefore unsuitable Tetrafluoroborat- anion is not stable and can decompose in the presence of suitable nucleophiles, such as traces of water, or at elevated temperature in fluoride and BF3, both of which interfere with alkoxylation. Fluoride is undesirable because of its toxicity as an impurity, BF3 can act as an alkoxylation catalyst and catalyze unwanted side reactions.

The invention thus provides a process for the preparation of DMC catalysts by reacting cyanometalate compounds, with metal salts, characterized in that the reaction is carried out in ionic liquids as a solvent or suspending agent.

The invention furthermore relates to the DMC catalysts prepared by the process according to the invention. The invention further relates to the use of the DMC catalysts prepared by the process according to the invention as a catalyst for the preparation of polyether alcohols by addition of alkylene oxides to H-functional starter substances.

The invention further provides a process for the preparation of polyether alcohols by catalytic addition of alkylene oxides to H-functional starter substances, characterized in that the catalysts of the invention DMC catalysts are used.

The invention further provides a process for the preparation of polyether alcohols by catalytic addition of alkylene oxides onto H-functional starter substances, characterized in that the catalysts of the invention DMC catalysts and is used as alkylene oxide in at least part of the addition of pure ethylene oxide.

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 having at least one cation and at least one anion, one of the ions, in particular the cation, being organic.

Ionic liquids in the sense of the present invention are (A) preferably salts of the general formula (I)

[A]; [Yf- (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 one, two or more -, tri- or tetravalent anion stands;

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

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

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] "- (IIb), where n = 3; or [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] "- (Nc), where n = 4 and

wherein [A ¹ J ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ and [Y] "- the meaning mentioned under (A) owns; or

(C) mixed salts of the general formulas (III)

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [M ¹ ] ⁺ [Y] "- (purple), where n = 4; [A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] n - (NIb), where n = 4;

[A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [M ³ ] ⁺ [Y] "- (Never), where n = 4;

[A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [Y] "- (II Id), where n = 3;

[A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] - (Never), where n = 3; [A ¹ J ⁺ [IVP] ⁺ [Y] - (Ulf), where n = 2;

[A ¹ ] ⁺ [A ² ] ⁺ [M ⁴ ] ²⁺ [Y] "- (NIg), where n = 4;

[A ¹ ] ⁺ [M ¹ ] ⁺ [M ⁴ ] ²⁺ [Y] "- (NIh), where n = 4;

[A ¹ J ⁺ [M ⁵ P ⁺ [Y] "- (MIi) where n = 4; or

[A ¹ J ⁺ [M ⁴ J ²⁺ [Y] "- (NIj) where n = 3 and

wherein [A ¹ ] ⁺ , [A ² J ⁺ and [A ³ J ^{+ are} independently selected from the groups mentioned for [A] ⁺ , [Y] "- has the meaning given under (A) and [M ¹ J ⁺ , [M ² J ⁺ , [M ³ J ⁺ monovalent metal cations, [M ⁴ J ²⁺ divalent metal cations and [M ⁵ J ³⁺ trivalent metal cations.

Preferably, the ionic liquids have a melting point of less than 180 ^° C. It is further preferred that the melting point is in a range from -50 ^° C. to 150 ^° C., more preferably in the range from -20 ^° C. to 120 ^° C., and still more preferably from - 20 ⁰ C to below 100 ⁰ C.

Compounds suitable for forming the cation [A] of ionic liquids are e.g. known 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, more preferably 1 to 5, most preferably 1 to 3 and especially 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 in order to generate 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 already 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 an ion exchanger or by displacement of the halide ion by a strong acid (to release the hydrohalic acid) happen. 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 6 -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 using such compounds as cations 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. Particular preference is given to those compounds which have at least one to six-membered heterocycle containing one, two or three nitrogen atoms and a sulfur or an oxygen atom, most preferably those having two nitrogen atoms. Preference is furthermore given to aromatic heterocycles, such as pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, pyrazolinium, imidazolium, thiazolium, oxazolium, pyrrolidinium and imidazolidinium.

Among these compounds, preference is given to those cations which have a molecular weight of less than 1000 g / mol, very particularly preferably less than 500 g / mol and in particular less than 250 g / mol.

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

(IVa) (IVb) (IVc)

(IVi) (IVj) (IVj ')

(IVm) (IVm ') (IVn)

(IVn ') (IVo) (IVo')

(IVp) (IVq) (IVq ')

(IVq ") (IVr) (IVr ')

(IVr ") (IVs) (IVt)

(IVu) (IVv) (IVw) and oligomers containing these structures.

Further suitable cations are compounds of the general formula (IVx) and (IVy) R ² R ²

3 1 -H ₁ I +.,

R-P-R S-R

I i

R R

(IVx) (IVy)

and oligomers containing this structure.

In the above formulas (IVa) to (IVy)

- 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 funkt-ionelle groups or substituted radical having 1 to 20 carbon atoms; and

- The radicals R ¹ to R ⁹ are each independently hydrogen, a sulfo group or an organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (IV) are bonded to a carbon atom (and not to a heteroatom), additionally may also stand for halogen or a functional group; or

two adjacent radicals from the series R ¹ to R ⁹ 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 or substituted radical with 1 to 30 carbon atoms.

As hetero atoms, in the definition of the radicals R and R ¹ to R ^{9, 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. Preferred groups which may be mentioned are in particular -O-, -S-, -SO-, -SO ₂ -, -NR'-, -N =, -PR'-, -PR ' ₂ and -SiRV, where the Radicals R 'is the remaining part of the carbon-containing radical. The radicals R ¹ to R ⁹ are, in the cases in which those in the above formulas (IV) to a carbon atom (and not to a heteroatom) bound 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-C4-alkyl) amino, Ci-C4-alkyloxycarbonyl or Ci-C4-alkyloxy.

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 sulphonic acid-substituted C 1 -C 20 -alkyl having in total 1 to 20 carbon atoms, such as, 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 - carbonyl) -ethyl, 2- (n-butoxy-carbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;

a residue derived from glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C 1 to C 1 alkyl as an end group, such as R ^A O- (CHR ^B -CH ₂ -O) _n -CHR ^B -CH ₂ - or

R ^A O- (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 preferably hydrogen, methyl or ethyl and n preferably O to 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-Ci- to Cβ-alkyl-amino, such as N, N-dimethylamino and N, N-diethylamino.

The radical R particularly preferably represents unbranched and unsubstituted C 1 - to C 18 -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 for 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 - where n is O to third

Preferably, the radicals R ¹ to R ⁹ are each independently

Hydrogen;

Halogen;

a functional group, in particular those as mentioned above;

- optionally interrupted 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;

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 -Ci8 alkenyl;

optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci ₂ -aryl;

optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci ₂ -cycloalkyl;

- optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci ₂ -cycloalkenyl; or

- a 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 having 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, a, a-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-am inobutyl, 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 _n F2 _(s -a) + (ib) H2a + b where n is 1 to 30, 0 < a <n and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C (n- ₂ ) F _{2 (n} - 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-but-oxyethyl, diethoxymethyl, diethoxyethyl, 2-lsopropoxyethyl, 2-butoxypropyl, 2-octyl oxyethyl, 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-dioxo-octyl, 1 1-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy 4-oxa-heptyl, 1 1-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5, 10-dioxa-tetradecyl, 5-methoxy-3- oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 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.

When 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- bis cis-alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _n F 2 ( _n ) - (ib) H 2a-b with n <30, 0 <a <n 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 C ₆ F ( _5-a ) Ha with 0 <a <5.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted Cs to Ci2-cycloalkyl is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl , diethylcyclohexyl, butyl tylcyclohexyl, methoxycyclohexyl, Dimethoxycyclohexyl, Diethoxycyclohexyl, butylthio cyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _n F2 _(n-a) - (ib) H2a-b where n <30, 0 <a <n and b = 0 or 1 and a saturated or unsaturated bicyclic system such as. Norbornyl or norbornenyl.

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-cyclohexa - dienyl or C _n F2 _(n-a) -3 (ib) H2a-3b where n <n 30, 0 <a <b and 0 or 1st

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-C4- 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;

unbranched or branched, unsubstituted or monosubstituted to hydroxyl, halogen, phenyl, cyano, d- to Cβ-alkoxycarbonyl and / or sulfonic acid-substituted Cr to Cis-alkyl having a total of 1 to 20 carbon atoms, such as 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- (ethoxycarbonyl) - ethyl, 2- (n-butoxycarbonyl) ethyl, trifluoromethyl, difluoromethyl, fluoromethane ethyl, 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 to C-alkyl end group, such as R ^A O- (CH R ^B -CH ₂ -O) n-CH R ^B -CH ₂ - or R ^A O- (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-trioxaundecyl, 3,6,9, 12-tetraoxatridecyl and 3,6,9 , 12-tetradeoxatradecyl;

Vinyl; and

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

Most preferably, the radicals R ¹ to R ⁹ 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, for 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) _n - CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _n -CH ₂ CH ₂ - where n is equal to 0 to 3.

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

one of R ¹ to R ^{5 is} methyl, ethyl or chlorine and the remaining 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 is} 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.

Very particularly preferred pyridinium ions (IVa) include 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-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium and 1- (1-octyl 1) -2-methyl-3-ethyl-pyridinium, 1- (1-dodecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-tetradecyl) -2-methyl-3-ethyl-pyridinium and 1 - (1-hexadecyl) -2-methyl-3-ethylpyridinium.

Very particularly preferred pyridazinium ions (IVb) are those 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 (IVc) 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 particularly preferred pyrazinium ions (IVd) are those 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 particular preference is given to using as imidazolium ions (IVe) 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, independently of one another, are hydrogen,

Methyl or ethyl.

Very particularly preferred imidazolium ions (IVe) 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- butyl imidazolium, 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) - 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-He xadecyl) -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 ethyl imidazolium, 3-butyl imidazolium, 1,4-dimethyl-3-octyl imidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethyl imidazolium, 1, 4,5-trimethyl-3-ethyl imidazolium , 1, 4,5-trimethyl-3-butylimidazolium and 1, 4,5-trimethyl-3-octylimidazolium.

Very particular preference is given as Pyrazoliumionen (IVf), (IVg) or (IVg ') such, in which

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

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

- R ¹ to R ^{4 are} independently hydrogen or methyl. Very particular preference is given as 1-pyrazolinium (IVi) such as those in which

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

Very particular preference is given to using 2-pyrazolinium ions (IVj) or (IVj ') as those in which

R ^{1 is} hydrogen, methyl, ethyl or phenyl, and R ² to R ^{6 are} independently of each other hydrogen or methyl.

Very particular preference is given to using as 3-pyrazolinium (IVk) or (IVk ') such, 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 as Imidazoliniumionen (IVI) 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 particular preference is given to imidazolinium ions (IVm) or (IVm ') 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 using as imidazolinium ions (IVn) or (IVn ') 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 thiazolium ions (IVo) or (IVo ') and oxazolium ions (IVp) as 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 1, 2,4-triazolium ions (IVq), (IVq ') or (IVq ") 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 (IVr), (IVr ') or (IVr ") 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 (IVs) are those in which

R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{9 are} independently hydrogen or methyl.

Very particular preference is given to using as imidazolidinium ions (IVt) 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 to using as ammonium ions (IVu) those in which

R ¹ to R ^{3 are} independently C ¹ to C 18 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 18 alkyl, 2-hydroxyethyl or 2-cyanoethyl.

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

Examples of the tertiary amines of which the quaternary ammonium ions of the general formula (IVu) are derived by quaternization with the abovementioned radicals R are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl-hexyl amine, 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-isopropylethylamine, di-isopropyl-n-propylamine, di-isopropyl-butylamine, diisopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, di-iso-propyl- 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, N n-butylpyrrolidine, N-sec-Butylpyrrodidin, N-tert-butylpyrrolidine, Nn-Pentylpyrrolidin, N methylcyclohexylamine ₁ N-di, N, N-diethylcyclohexylamine, N, N-Di-n -butylcyclohexylamine, Nn-propylpiperidine, N-isopropylpiperidine, Nn-butylpiperidine, 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-iso-propylaniline, 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 (IVu) are di-iso-propylethylamine, diethyl-tert-butylamine, diisopropyl-propylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines 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 particular preference is given to using as guanidinium ions (IVv) those in which

- R ¹ to R ^{5 are} methyl.

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

Very particular preference is given to using as cholinium ions (IVw) 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 are} OH or -PO (OH) ₂ .

Particularly preferred cholinium ions (IVw) are those in which R ^{3 is} selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa- octyl, 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-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxo-octyl, 11- Ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-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 (IVx) are those in which

- R ¹ to R ^{3 are} independently of each other Ci-cis-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-Do - decyl) -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-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium, 1- (1-octyl) -2-methyl-3-ethyl- pyridinium, 1 - (1 -Dode cyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethylpyridinium, 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium, 1 Methyl imidazolium, 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-methyl-imidazolium, 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-tetramethylimida - zolium, 1, 4,5-trimethyl-3-ethylimidazolium, 1, 4,5-trimethyl-3-butylimidazolium and 1, 4,5-trimethyl-3-octylimidazolium. The metal cations [IVP] ⁺ , [M ² ] ⁺ , [M ³ ] ⁺ , [M ⁴ P ⁺ and [M ⁵ J ³⁺ mentioned in formulas (IIIa) to (NIj) are generally metal cations the 1st, 2nd, 6th, 7th, 8th, 9th, 10th, 11th, 12th and 13th group of the periodic table. Suitable metal cations are, for example, Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Cr ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Ni ²⁺ , Cu ^{2 +} , Ag ⁺ , Zn ²⁺ and Al ³⁺ .

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

The anion [Y] ⁿ "of the ionic liquid is for example selected from

the group of halides and halogen-containing compounds of the formula: Cl, Br, I, AICI ₄ , Al ₂ Cl ₇ ^" , Al ₃ CII ₀ -, AIBr ₄ ^" , FeCl ₄ ^" , BCk ₁ ZnCl ₃ ^" , SnCl ₃ ^" , CuCl ₂ ^" , CF ₃ SO ₃ ^" , (CF ₃ SO ₂ ) ₂ N ^" , CF ₃ CO ₂ -, CCI 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 -, R ³ OSO 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 PO-, 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 ), excluding tetrafluoroborate as an anion,

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

- the group of carbonates and carbonic esters of the general formula: HCO ₃ -, CO ₃ ² -, R ³ CO ₃ - - 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 ^a R ^b Si0 ₄ ² -, R ^a 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 Si0 ₃ -, R ³ R ^b R ^c Si0 ₂ -, R ³ R ^b Si0 ₃ ² -

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

the group of methides of the general formula:

SO ₂ -R ³

R ^b -O ₂ S ^' SO, -R ^C

- the group of alkoxides and aryloxides of the general formulas: R ³ O-;

the group of halometalates of the general formula [M _q HaL] ^s -, where M is a metal and Hal is chlorine, bromine or iodine, q and r are positive integers indicating the stoichiometry of the complex and s is a whole positive number and indicates the charge of the complex;

- the group of sulfides, hydrogen sulfides, polysulfides, hydrogen polysulfides and thiolates of the general formulas:

S ² -, HS-, [Sv] ² -, [HSv] -, [R ³ S] -, wherein v is a whole positive number from 2 to 10;

the group of complex metal ions such as Fe (CN) 6 ^{3 "} , Fe (CN) 6 ^4" , MnO ₄ -, Fe (CO) ₄ -

Where R ³ , 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 atoms. and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C2-Ci8-alkyl, Cβ-Cu-Arvl, C5-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle in which two of them together may form an unsaturated, saturated or aromatic ring optionally 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.

In which are optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted Ci-cis-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-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-dioxolane-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-methoxyisopropyl, 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-dimethyla 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 θ-ethoxyhexyl.

Optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C2-Ci8-alkyl, 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-oxononyl, 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, 11-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, 11-ethoxy-3,6,9- trioxaundecyl, 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 used 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-Ci-C4-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 mean.

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, Cyano or CrC ₄ -alkoxy. In this case, Ci to C ₄ -AlkVl 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 ethoxymethylphenyl.

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, methoxycyclo lohexyl, 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, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxifuryl , Dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.

As the ionic liquid in the sense of the invention, substances with a soft cation and / or a soft anion are preferably used. This means that cations and / or anions are well stabilized, for example by inductive and / or mesomeric effects. Cations preferably have electron-donating substituents. Preferably, the cation contains only electron-donating substituents. The anion preferably has electron-withdrawing substituents. In this case, it is particularly preferred to use an ionic liquid in which the charge of the cation, of the anion or of the cation and of the anion is delocalized by mesomeric effects. As cations therefore imidazolium, guanidinium or pyrazole derivatives are preferred. Particular preference is given to ionic liquids according to the invention having cations selected from the group comprising 1, 2,3-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,3,4-dimethylimidazolium, 1,3,4-trimethyl - Imidazolium, 1, 3-dibutyl-2-methylimidazolium, 1, 3-dibutylimidazolium, 1, 2-dimethylimidazolium, 1, 3-dimethylimidazolium, 1-benzyl-3-methylimidazolium, 1-butyl-2,3-di - methylimidazolium, 1-butyl-2-ethyl-5-methylimidazolium, 1-butyl-2-ethylimidazolium, 1-butyl-2-methylimidazolium, 1-butyl-3,4,5-trimethylimidazolium, 1 -butyl-3,4 dimethyl imidazolium, 1-butyl-3-ethylimidazolium, 1-butyl-3-methylimidazolium, 1-butyl-4-methylimidazolium, 1-butylimidazolium, 1-decyl-3-methylimidazolium, 1-dodecyl-3-methylimidazolium , 1-ethyl-2,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-hexadecyl-2,3-dimethylimidazolium, 1-hexadecyl-3-methylimidazolium, 1 -hexyl-2,3-dimethylimidazolium, 1-hexyl 3-methylimidazolium, 1-methyl-2-ethylimidazolium, 1-methyl-3 octylimidazolium, 1-methylimidazolium, 1-pentyl-3-methylimidazolium, 1-phenylpropyl-3-methylimidazolium, 1-propyl-2,3-dimethylimidazolium, 1-tetradecyl-3-methylimidazolium, 2,3-dimethylimidazolium, 2-ethyl 3,4-dimethylimidazolium, 3,4-dimethylimidazolium, 1, 2-dimethylpyridinium, guanidinium, hexamethylguanidinium, N, N, N ', N'-tetramethyl-N'-ethylguanidinium, N-pentamethyl-N-isopropylguanidinium, N-pentamethyl-N-propylguanidinium, benzyltriphenylphosphonium, tetrabutylphosphonium, trihexyl (tetradecyl) phosphonium and tri-iso-butyl (methyl) phosphonium.

Even more preferred cations are selected from the group containing 1, 2,3-trimethylimidazolium, 1,2-dimethylimidazolium, 1-butyl-2-methylimidazolium, 1-butyl-4-methylimidazolium, 1,3-diethylimidazolium, 1-benzyl 3-methylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-butyl-2-methylimidazolium, 1-butyl-3-ethylimidazolium, 1-butyl-3-methylimidazolium, 1-butylimidazolium, 1-ethyl-2,3 dimethyl imidazolium, 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-methyl-2-ethylimidazolium, 1-methyl-3-octylimidazolium, 1-methylimidazolium, 1-decyl-3-methylimidazolium, 1-dodecyl-3-methylimidazolium, guanidinium, N, N, N ', N'-tetramethyl-N'-ethylguanidinium, benzyltriphenylphosphonium and tetrabutylphosphonium.

In particular, the cations are selected from the group comprising 1, 2,3-trimethylimidazolium, 1, 2-dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-butyl-3-methylimidazolium, 1-ethyl-2, 3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-butylimidazolium and 1-methylimidazolium.

The anions are preferably selected for the process according to the invention from the group comprising acetate, bis (2,4,4-trimethylpentyl) phosphinate, bis (malonato) borate, bis (oxalato) borate, bis (phtalato) borate, bis ( salicylato) borate, bis (trifluoromethanesulfonyl) imidate, bis (trifluoromethyl) imidate, borate, bromide, bromoaluminates, carbonate, chloroaluminates, decylbenzenesulfonate, dichlorocuprate, dicyanamide, didecylbenzenesulfonate, didodecylbenzenesulfonate, diethylphosphate, dihydrogenphosphate, dodecylbenzenesulphonate, Ethyl sulfate, ethyl sulfonate, hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, hydrogen sulfite, iodide, methyl sulfate, methyl sulfonate, nitrate, nitrite, phosphate, sulfite, tetracyano borate, tetrakis (hydrogensulfato) borate, tetrakis (methylsulfonate) borate, thiocyanate, tosylate, trichlorozincate, trifluoroacetate , Trifluromethylsulfonate.

To prepare the DMC catalysts, the metal salt and the cyanometalate compound are dissolved or suspended in the ionic liquids and these solutions or suspensions are reacted with one another.

Preferred metal salts are compounds of the general formula (VI)

used, where

M ^{1 is} a metal ion selected from the group comprising Zn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ ,

Co ³⁺ , Ni ²⁺ , Mn ²⁺ , Sn ²⁺ , Sn ⁴⁺ , Pb ²⁺ , Al ³⁺ , Sr ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , La ³⁺ , Ce ^{3 +} , Ce ⁴⁺ ,

Eu ³⁺ , Mg ²⁺ , Ti ⁴⁺ , Ag ⁺ , Rh ²⁺ , Ru ²⁺ , Ru ³⁺ , Pd ²⁺

X is an anion selected from the group comprising halide, hydroxide, sulfate, hydrogensulfate, carbonate, bicarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (NO 2 O) or a mixture of two or more of the above anions or a mixture of one or more of the abovementioned anions with one of the uncharged species selected from CO, H2O and NO,

g, n, are selected to ensure electroneutrality. As cyanometalate compounds are preferably compounds of general formula (V)

used, where

M ^{2 is} a metal ion selected from the group containing Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ ,

Mn ²⁺ , Mn ³⁺ , Ni ²⁺ , Cr ²⁺ , Cr ³⁺ , Rh ³⁺ , Ru ²⁺ , Ir ³⁺ and M ¹ and M ^{2 are} identical or different,

M ^{3 is} hydrogen or an alkali or alkaline earth metal or ammonium [NR ₄ J ⁺ with R = hydrogen, alkyl or aryl,

b, d, are selected to ensure electroneutrality.

Whether working in solution or in suspension depends on the solubility of the component in the ionic liquid. Both modes of operation are to be regarded as equivalent within the meaning of the present invention.

To carry out the process according to the invention, a solution or suspension of a compound (V) in an ionic liquid is combined with the solution or suspension of a metal salt (VI) in an ionic liquid. This can be done with a stoichiometric excess of the metal salt. Preferably, the molar ratio of the metal ion to the cyanometalate component is from 1.1 to 7.0, preferably from 1.2 to 5.0 and particularly preferably from 1.3 to 3.0. It is advantageous to introduce the metal salt solution and add the cyanometalate compound, but it can also be reversed procedure. During and after the combination of the educt solutions, thorough mixing, for example by stirring, is necessary.

The content of the compound (V) in the solution based on the mass of the solution is 0.1 to 30 wt .-%, preferably 0.1 to 20 wt .-%, in particular 0.2 to 10 wt .-%. The content of the metal salt component in the metal salt solution, based on the mass of metal salt solution, is from 0.1 to 50% by weight, preferably from 0.2 to 40% by weight, in particular from 0.5 to 30% by weight.

At least one of the solutions of the starting materials may include a heteroatom-containing ligand, as denoted and illustrated in the general formula (VI) as L and is explained. The ligands containing heteroatoms can also be added to the resulting suspension only after the two starting materials have been combined, and good mixing must also be ensured here. The content of the ligands containing heteroatoms in the suspension formed after the precipitation should be 1 to 60% by weight, preferably 5 to 40% by weight, in particular 10 to 30% by weight.

In order to adjust the morphology of the multimetal cyanide compounds, it has proven useful to carry out the preparation of these compounds in the presence of surface-active substances. The surface-active substances are usually already presented in at least one of the two solutions. The surface-active substances are preferably added to the solution which is initially introduced during the precipitation. The content of surface-active substances in the precipitation suspension based on the total mass of the precipitation suspension is preferably between 0.01 and 40 wt .-%, in particular between 0.05 to 30 wt .-%. A further preferred embodiment provides that the surface-active substances are distributed proportionally to the two educt solutions.

After precipitation, the multimetal cyanide compounds thus produced can be separated from the precipitation suspension, for example by filtration or centrifugation. One or more washes of the multimetal cyanide compounds can then follow this separation. The washings may be carried out with ionic liquids or "conventional" organic solvents such as alcohols, alkanes, haloalkanes, nitriles, ethers, esters, etc. The washings may be carried out on the separation device (eg filter device) itself or in separate apparatuses by, for example, resuspending the multimetal cyanide compound in washing liquid and again separating it from the liquid. This washing can be carried out at temperatures of 10 ^° C. to 180 ^° C., preferably 15 ^° C. to 60 ^° C.

The multimetal cyanide compound thus obtained is separated off, for example by filtration or centrifugation, and optionally, for example when washing with a "conventional" organic solvent, dried at ambient pressure or reduced pressure at temperatures between ambient and 120 ⁰ C in suitable , Known to those skilled in the art, carried out.

The DMC catalysts prepared by the process according to the invention preferably have a structure which can be described by the general formula (VII)

M ¹ χM ³ _y [M ² (CN) _b ] zh (IL) -k (L) (VII),

wherein, IL is the ionic liquid and L is the solvent of the wash and the rest of the symbols have the meaning described above or x, y, z selected so are that the electron neutrality is ensured and x and z are greater than zero, y can also be zero and h and k can assume values between 0.01 and 10.

The D MC catalysts prepared by the process according to the invention may be crystalline, partially crystalline or amorphous.

The DMC catalysts according to the invention are used as catalysts for the preparation of polyether alcohols. In this case, the DMC catalysts can be used as a powder or in the form of a suspension, in particular in an alcohol. As alcohols for the suspension in particular polyhydric alcohols or poly-ether alcohols are used. Particular preference is given to using the alcohols which are used as starter substances for the preparation of the polyether alcohols.

In particular, polyether alcohols having functionalities of 1 to 8, preferably 1 to 6 and molar masses M _w of 500 to 50,000, preferably 800 to 15,000 are prepared by addition of alkylene oxides onto H-functional starter substances by means of the DMC catalysts according to the invention. The catalyst concentrations used are less than 1 wt .-%, preferably less than 0.5 wt .-%, more preferably less than 1000 ppm, more preferably less than 500 ppm, more preferably less than 100 ppm, based on the total mass of the polyetherol. The preparation of the polyetherols can be carried out either continuously or discontinuously. The temperatures used in the synthesis are between 50 ⁰ C and 200 ⁰ C, with temperatures between 90 ⁰ C and 150 ⁰ C are preferred.

For the preparation of the polyether alcohols using the catalysts according to the invention, it is possible to use compounds having at least one epoxy group, for example ethylene oxide, 1,2-epoxypropane (propylene oxide), 1,2-methyl-2-methylpropane, 1,2-epoxybutane (butylene oxide) , 2,3-epoxybutane, 1,2-methyl-3-methylbutane, 1,2-epoxy pentane, 1,2-methyl-3-methylpentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane , 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, styrene oxide, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, (2,3-epoxypropyl) benzene, Vinyl oxirane, 3-phenoxy-1,2-epoxypropane, 2,3-epoxy methyl ether, 2,3-epoxyethyl ether, 2,3-epoxy isopropyl ether, 2,3-epoxy-1-propanol, (3,4-epoxybutyl) stearate , 4,5-epoxypentylacetate, 2,3-epoxypropane methacrylate, 2,3-epoxypropane acrylate, glycidyl butyrate, methyl glycidate, ethyl 2,3-epoxybutanoate, 4- (trimethylsilyl) butane-1,2-epoxide, 4- (triethylsilyl) butane -1, 2-epoxide, 3- (perfluoromethyl) propene oxide, 3- (perfluoroethyl) propene oxide, 3- (perfluorobutyl) propene oxide, 4- (2,3-epoxypropy) morpholine, 1- (oxiran-2-ylmethyl) pyrrolidin-2-one, as well as any mixtures thereof, are used.

Preference is given to ethylene oxide, propylene oxide, butylene oxide, styrene oxide, vinyl oxirane and any desired mixtures thereof with one another, in particular ethylene oxide, propylene oxide, and mixtures of ethylene oxide and propylene oxide. The polyether alcohols according to the invention usually have a functionality of 2 to 8, preferably 2 to 4 and in particular 2 to 3 and an equivalent weight of greater than 500 g / mol. As starting substances are used as higher-functional starter substances in particular sugar alcohols, such as sorbitol, hexitol and sucrose, but mostly di- and / or trifunctional alcohols or water, either as a single substance or as a mixture of at least 2 of said starting substances used. Examples of two-functional starting substances are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol-1, 4 and pentanediol-1, 5. Examples of tri-functional starter substances are trimethylolpropane, pentaerythritol and in particular glycerol. The starting substances can also be used in the form of alkoxylates, in particular those having a molecular weight M _w in the range of 62 to 15,000 g / mol. These alkoxylates can be prepared in a separate process step, wherein other catalysts than multimetal cyanide compounds, for example alkali metal hydroxides, can be used for their preparation. When using alkali metal hydroxides to prepare the alkoxylates, it is necessary to remove the catalyst almost completely since alkali metal hydroxides can deactivate the multimetal cyanide catalysts. The advantage of using alkoxylates as starter substances is the faster initiation of the reaction; the disadvantage is the introduction of an additional process step and, as stated, the expensive purification of the alkoxylate if appropriate.

In a preferred embodiment of the preparation of the polyether alcohols, these have a block of pure ethylene oxide units, which is particularly preferably located at the chain end.

The catalysts prepared by the process according to the invention also surprisingly permit the incorporation of pure ethylene oxide units in the polyether chain, in particular at the chain end.

The direct introduction of an end block of ethylene oxide units with the DMC catalysts according to the invention represents a simplified procedure, because the additional step of catalyst replacement is omitted. The addition of, for example, aqueous potassium hydroxide solution and the subsequent removal of the water is therefore not necessary before further reaction with ethylene oxide.

Polyether alcohols having an endblock of ethylene oxide units are particularly important for foam applications. Because of the high number of primary OH groups, the polyols have a markedly increased reactivity due to the terminal block of ethylene oxide units, and the subsequent reaction with the isocyanate component takes place much more rapidly. For the production of flexible foam polyurethane, the two components, polyetherol and isocyanate, are introduced into a optionally preheated mold having a complex geometry, sprayed. For a short demolding time, therefore, a fast reaction of the components is necessary.

The invention will be described in more detail in the following examples:

Examples

In carrying out the examples, all solvents used were dried over MoI sieve (3Ä).

a) Catalyst preparation

example 1

5.5 g Hexacyanokobaltsäure were incubated at 90 ⁰ C in 50 g Butylmethylimidazoliumacetat (BMIM OAc) dissolved. 9.0 g of ZnSO ₄ -H ₂ O were dissolved at 1 10 ⁰ C in 50 g BMIM OAc and added dropwise via a heated dropping funnel (110 ⁰ C) within 10 minutes to the presented in a beaker Hexacyanokobaltsäurelösung. The research Reaktionsmi- 90 minutes at 90 ⁰ C was stirred. After cooling and addition of 1200 g of methanol, the resulting suspension was stored overnight at 5 ⁰ C and then removed by centrifugation. Thereafter, the product was resuspended in 370 g of methanol, centrifuged again and then dried at 40 ⁰ C for 48 hours in air. The DMC catalyst thus obtained contained 9.6% Co, 20.7% Zn and 34.4% C according to elemental analysis.

Example 2

6.5 g Hexacyanokobaltsäure were dissolved at 90 ⁰ C in 50 g methylimidazolium chloride (HMIM Cl). 37.9 g of zinc stearate were suspended in 120 g of HMIM Cl and added portionwise to the hexacyanocobaltic acid solution in a beaker within 10 minutes. The reaction mixture was stirred at 90 ^° C. for 90 minutes. After cooling and addition of 1300 g of methanol, the resulting suspension was stored overnight at 5 ⁰ C and then filtered off. Thereafter, the product was resuspended six times in 400 ml of methanol, each filtered off and then dried for 16 hours at 60 ⁰ C in vacuo. The DMC catalyst thus obtained contained 6.5% Co, 13.9% Zn and 48.1% C according to elemental analysis.

b) Preparation of the polyether alcohols

Example 3 There was a 5.8% strength catalyst suspension in a triol / diol mixture, which was propoxylated by DMC technology to an OH number of about 142 mg KOH / g and from the Seitz depth filter, the catalyst was completely removed by addition the required amount of D MC catalyst from Example 1 to the triol / diol mixture produced. The suspension obtained was homogenized with the aid of a Turrax (model: Ultra Turrax T25, manufacturer: IKA) at the lowest level (11,000 rpm) for 10 to 15 minutes. The resulting suspension was freed from water for 6 to 12 hours at 80 to 100 ⁰ C on a rotary evaporator under a slight vacuum.

0.32 g of the suspension were placed in an autoclave and mixed with 70.0 g of the triol / diol mixture. The reactor was sealed, evacuated and pressurized with nitrogen to 400-800 mbara. The stirrer was operated at a speed of 500 rpm. It was heated to 130 ⁰ C and pressed nitrogen to a pressure of 3 to 4 bara. After a successful pressure test for 15 minutes, the gas was decompressed and evacuated to 10 to 50 mbara. The reaction mixture was then reacted with 161.4 ml (134.2 g) of propylene oxide. To this end, 25 ml of the total amount of propylene oxide was added at a rate of 2.5 ml / min to ensure the onset of the reaction. The light-off temperature was about 150 ⁰ C at a pressure of 2.35 bara. After the temperature was again set to 130 ⁰ C, in the second stage, the flow rate of propylene oxide was successively raised and the remaining 136.4 ml of propylene oxide added. After complete addition of the propylene oxide, the post-reaction (about 2 h) was carried out to a constant final pressure of 1.55 bara. The resulting OH number of the final product was 51.2 mg KOH / g. The viscosity was 567 mPa.s and the DMC content was 106 ppm.

Example 4

It was prepared as described in Example 3, a 5.18% catalyst suspension of the catalyst of Example 2 in the triol / diol mixture. Of which were

2.00 g presented in an autoclave and treated with 70.0 g of the triol / diol mixture. The reaction mixture was first mixed with 25 ml of propylene oxide as described in Example 3 with a flow rate of 2.5 ml / min at 130 ⁰ C to ensure the onset of the reaction. The light-off temperature was about 150 ⁰ C and the pressure at 3.15 bara. In the second stage, a pressure of 3.7 bar at 130 ⁰ C was first pressed with nitrogen for safety reasons. Subsequently, 132.0 ml (1.175 g) of ethylene oxide were metered in at a flow rate between 0.8 ml / min and 1.5 ml / min. After complete addition of the ethylene oxide, the post-reaction (about 1 1, 5 h) was carried out to a constant final pressure of 4.46 bara. The resulting OH number of the final product was 52.1 mg KOH / g. The viscosity was 1783 mPa.s and the DMC

Content 565 ppm. The ¹ H NMR analysis revealed a total content of about 46% of propylene oxide and about 54% ethylene oxide in the product and the content of primary OH groups was 88% (reaction with trichloroacetyl isocyanate and ¹ H NMR).

Claims

claims

1. A process for preparing DMC catalysts by reacting cyano metalate compounds with metal salts, characterized in that the reaction is carried out in ionic liquids as a solvent or suspending agent.

2. The method according to claim 1, characterized in that the ionic liquids have a melting point of below 100 ⁰ C.

3. The method according to claim 1, characterized in that the ionic liquids have a melting point of below 80 ⁰ C.

4. The method according to claim 1, characterized in that the ionic liquids have a melting point of below 50 ⁰ C.

5. The method according to claim 1, characterized in that the ionic liquids have at least one cation and at least one anion, wherein one of the ions is organic.

6. The method according to claim 2, characterized in that the cation is organic.

7. The method according to claim 2, characterized in that the anion is organic.

8. The method according to claim 1, characterized in that the ionic liquids have the general formula (I)

[A]; [Yf- (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 is a di, tri or tetravalent anion;

9. The method according to claim 1, characterized in that the ionic liquids one of the general formulas (II)

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

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] "- (Nc), 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.

10. The method according to claim 1, characterized in that the ionic liquids one of the general formulas

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [M ¹ ] ⁺ [Y] "- (purple), where n = 4;

[A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] - (NIb), where n = 4; [A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [ M ³ ] ⁺ [Y] "- (Never), where n = 4;

[A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [Y] "- (NId), where n = 3;

[A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] "- (Never), where n = 3;

[A ¹ J ⁺ [IVP] ⁺ [Y] "- (Nif), where n = 2;

[A ¹ ] ⁺ [A ² ] ⁺ [M ⁴ ] ²⁺ [Y] "- (NIg), where n = 4; [A ¹ ] ⁺ [M ¹ ] ⁺ [M ⁴ ] ²⁺ [Y]" - (NIh), where n = 4;

[A ¹ ] ⁺ [M ⁵ ] ³⁺ [Y] "- (MIi), where n = 4; or

[A ¹ J ⁺ [M ⁴ J ²⁺ [Y] "- (NIj) where n = 3 and

wherein [A ¹ ] ⁺ , [A ² J ⁺ and [A ³ J ^{+ are} independently selected from the groups mentioned for [A] ⁺ , [Y] "- has the meaning mentioned under (A) and

[M ⁺ ¹ J, [M ² J ^+, [M ³ ⁺ J monovalent metal cations, [M ⁴ J ^{2+ is a} divalent metal cations and [M ⁵ Y ^{3+ is a} trivalent metal cations comprise mean.

1 1. A method according to claim 1, characterized in that are used as metal salts of those of the general formula (Vl),

in which

M ^{1 is} a metal ion selected from the group consisting of Zn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Ni ²⁺ , Mn ²⁺ , Sn ²⁺ , Sn ⁴⁺ , Pb ²⁺ , Al ³⁺ , Sr ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , La ³⁺ , Ce ³⁺ , Ce ⁴⁺ , Eu ³⁺ , Mg ²⁺ , Ti ⁴⁺ , Ag ⁺ , Rh ^{2 +} , Ru ²⁺ , Ru ³⁺ , Pd ²⁺

X is an anion selected from the group consisting of halide, hydroxide,

Sulfate, hydrogen sulfate, carbonate, bicarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (NO 2 -) or a mixture of two or more of the abovementioned anions or a mixture of one or more of the abovementioned ions with one of the uncharged species selected from CO, H2O and

NO, is and g, n, are selected to ensure electroneutrality.

12. The method according to claim 1, characterized in that as cyanometalate compounds of the general formula (V) are used,

in which

M ^{2 is} a metal ion selected from the group containing Fe ²⁺ , Fe ³⁺ , Co ²⁺ ,

Co ³⁺ , Mn ²⁺ , Mn ³⁺ , Ni ²⁺ , Cr ²⁺ , Cr ³⁺ , Rh ³⁺ , Ru ²⁺ , Ir ³⁺ and M ¹ and M ^{2 are} identical or different,

M ^{3 is} hydrogen or an alkali or alkaline earth metal or ammonium [NR ₄ J ⁺ with R = hydrogen, alkyl or aryl, and

b, d, are selected to ensure electroneutrality.

13. DMC catalysts of the general formula (VII)

M ¹ χM ³ _y [M ² (CN) b] zh (IL) -k (L) (VII),

where, IL is the ionic liquid and L is the solvent of the wash and the remainder of the symbols have the meaning described above or x, y, z are chosen such that the electron neutrality is ensured and x and z are greater

Are zero, y can also be zero and h and k can assume values between 0.01 and 10, producible according to one of claims 1 to 12.

14. A process for the preparation of polyether alcohols by catalytic addition of alkylene oxides to H-functional starter substances, characterized in that are used as catalysts DMC catalysts according to claim 13.

15. The method according to claim 14, characterized in that at least at a nem part of the addition of pure ethylene oxide is deposited.

16. The method according to claim 15, characterized in that the addition of pure ethylene oxide takes place at the chain end.