WO2008119770A1 - Method for modifying the structure of a cellulose material by treatment with an ionic liquid - Google Patents

Abstract

The present invention relates to a method for modifying the structure of a cellulose material, wherein said material is brought in contact with a liquid treatment medium that comprises at least one ionic liquid.

Description

 METHOD FOR MODIFYING THE STRUCTURE OF A CELLULOSE MATERIAL THROUGH TREATMENT WITH AN IONIC LIQUID

description

The present invention relates to a method of modifying the structure of a cellulosic material by contacting it with a liquid treatment medium comprising at least one ionic liquid.

With a share of approximately 700 billion tonnes of the estimated biomass supply of 1.5 trillion tonnes on earth, cellulose is the most important representative in the group of organic biopolymers and a very versatile raw material. Wood pulp derived from wood, which is predominantly obtained by mechanical means, serves as fibrous material for the production of paper and paper-like products, such as cardboard and cardboard. Made of wood or other fiber materials by digestion pulp containing a very high proportion of cellulose, the z. Currently the most important raw material base for the production of paper, cardboard, cellulose regenerated fibers and foils. Cellulose is also the most important constituent of fiber raw materials, especially cotton, for the textile industry. Cellulose is a generally highly crystalline biopolymer of B-anhydroglucopyranose with long chains of sugar units linked by β-1,4-glycosidic linkages. The individual polymer chains are interconnected by inter- and intramolecular hydrogen bonds and Van der Wals interactions. The structure of unmodified clusters is further characterized by a high proportion of crystalline regions. With this structure, certain application properties are associated, which are still in need of improvement due to the extremely diverse applications of cellulose materials. So it may be z. For example, it may be desirable to vary mechanical properties of the material such as strength or porosity, optical properties such as color or gloss, and / or surface properties such as roughness, grip, or air resistance.

It is known to completely dissolve cellulosic materials in order to subject them to a physical or chemical treatment process.

It is known to use as solvent for cellulose various ionic liquids. Thus, S. Zhu et al. in Green Chem. 2006, 8, p. 325 - 327, in general, the possibility of dissolving cellulose in ionic liquids and recovering it by adding suitable precipitants, such as water, ethanol or acetone. Specifically, suitable ionic liquids are 1-butyl-3-methylimidazolium chloride (BMIMCI) and 1-allyl-3-methylimidazolium chloride (AMIMCI). WO 03/029329 teaches to dissolve cellulose for its further processing in an ionic liquid which may essentially contain no water and no nitrogenous bases.

WO 2004/084627 describes a process for the preparation of regenerated cellulose capsules with an active ingredient using an ionic liquid as a solvent.

WO 2005/017001 describes a method for dissolving a lignocellulosic material with an ionic liquid under microwave irradiation and / or pressure and in the absence of water. The cations of the ionic liquid correspond to those mentioned in WO 2004/084627.

WO 2005/017252 describes a method for treating a lignocellulosic material with an ionic liquid, for. B. for delignification.

DE 102005017733 describes solutions containing cellulose, an ionic liquid as solvent and 6 to 30 wt .-% of a nitrogen-containing base, based on the total weight of the solution.

DE 10 2005 017 715 describes solutions containing cellulose and an ionic liquid, wherein the ionic liquid is based on cations which have at least one atom selected from nitrogen, oxygen, sulfur and phosphorus and which is present in protonated form.

A fundamental problem in the provision of solutions of various cellulosic materials, which contain other components in addition to cellulose, is the insufficient solubility of these additional components, which necessitate the use of very specific ionic liquids, larger amounts of solvent and / or drastic solution conditions. The recovery of the ionic liquid used as a solvent is associated with additional technical effort.

Surprisingly, it has now been found that in order to modify the structure of cellulosic materials and the concomitant modification of the properties, it is sufficient to bring the cellulosic material into contact with an amount of ionic liquid which is insufficient to completely render the cellulosic material in a solubilized state convict.

The invention therefore provides a method of modifying the structure of a cellulosic material by contacting it with a liquid treatment medium comprising at least one ionic liquid, wherein the bulk of the cellulosic material is not converted to a solubilized state. The inventive method in its embodiments described below is advantageous with respect to one or more of the following points:

The complete dissolution of the cellulosic material is undesirable in many cases, since only a modification of the structure, but not its complete destruction is sought.

The amounts of ionic liquid used are significantly lower than in a complete solution of the cellulosic material, thus reducing the cost of recovery or the ionic liquid used may remain in the modified cellulosic material.

The inventive method is particularly suitable for modifying the properties of paper and paper-like products or of cellulose starting materials for the production of paper and paper-like products. The resulting products are z. B. by increased strength, reduced porosity and / or lower air resistance.

The term "modification of the structure" is to be understood broadly in the context of the present invention and in principle refers to any structural change associated with the change of at least one physical property of the cellulosic material.

Typical physical properties that undergo a change in a modification of the structure according to the inventive method are the so-called material properties, which can generally be described qualitatively by so-called material parameters. Typical material properties are:

In a specific embodiment, the method according to the invention serves to modify the structure of paper or of a cellulose material, which is subsequently used for papermaking. Typical characteristics for paper that may change with a modification of the structure are the following:

1. area-related mass

2nd thickness

3. specific volume

4. Breaking strength

5. Elongation at break

6. Width-related breaking force

7. Breaking force index

8. Tear length

9. Tear work

10. Air resistance

1 1. Porosity

1. Area-related mass

The basis weight can be determined according to DIN ISO 536. It results from the quotient of mass and area of a sample and is given in [g / m ² ].

2nd thickness

The thickness is usually defined by the measuring instrument used. According to DIN 53105, part 1 z. For example, the meter must have two plane-parallel plates of 200 mm ² each, which act at 100 kPa on the sample. The distance between the plates is then the paper thickness.

3. Specific volume The ratio of the thickness of a paper to its weight is called the specific volume.

4th to 8th breaking strength, breaking elongation, breaking length, width-related breaking force, breaking strength index

In the tensile test according to DIN EN ISO 1924-2 (old: DIN 53112), breaking strength, elongation at break and width-related breaking force are determined. From the breaking force F _B , the breaking length R can be derived, knowing the width b of the test strip and its area-related mass niA:

D max o

G

with Fmax, the breaking force in N and the initial length L ₀ in meters, the weight of the paper strip G (at 15 mm width and 65% relative humidity). The tear length R results in m.

Under the tear length R is understood in paper, the length of the strip, in which the strip, suspended on one side, tearing off by its own weight at the suspension point.

From the mean values of the measured width-related breaking force and the area-related mass, the breaking strength index I.

9. Tear work

The work necessary to stretch and tear the sample is called tearing

where ^ is the degree of fill and ^{B is} the elongation at break Δ | _ at F _ma χ.

The degree of perfection can be calculated from the force-strain diagram by dividing the area under the curve by the area that results when constructing a rectangle between the zero and the break point. The humidity has an influence on the measured values. Correctly according to DIN, the samples should be brought to 65% moisture before this test. It is also possible to measure the humidity and to correct the measured values with empirically determined correction factors from tables. 10. Air resistance

Air resistance is the resistance that a sheet of paper opposes to the passage of air when there is a pressure differential between the boundaries of the sample. The air resistance measurement can be done in a Gurley Method densitometer by measuring, for a given volume of air, the time it takes to pass through a sample of given dimensions under standard conditions of pressure, pressure difference, temperature and relative humidity.

According to the invention, the treatment of the cellulosic material with a liquid treatment medium is carried out under such conditions that the bulk of the cellulosic material is not converted to a solubilized state. By "main amount" is meant that at least 30 wt .-%, preferably at least 50 wt .-% of the cellulose material used for the treatment is not converted into the solubilized state. Preferably, at least 75% by weight, especially at least 90% by weight, of the cellulosic material is not converted to a solubilized state.

The term "solubilization" in the context of the invention refers to the conversion into a liquid state and in this case comprises the generation of solutions of the cellulose material as well as the conversion into a different solubilized state. If a cellulosic material is converted into a solubilized state, the individual polymer molecules do not necessarily have to be completely surrounded by a solvate shell. It is essential that the polymer changes to a liquid state as a result of the solubilization.

Prevention of solubilization of a major amount of the cellulosic material is accomplished by one or more of the following measures:

Using an amount of the liquid treatment medium insufficient to solubilize the bulk of the cellulosic material;

Carrying out the treatment at a low treatment temperature, preferably upstream of at most 100 ⁰ C, particularly preferably of at most 70 ⁰ C, in particular of at most 50 ⁰ C;

Performing the treatment for a treatment time that is insufficient to convert the majority of the cellulosic material to a solubilized state; Use of a treatment medium which comprises at least one ionic liquid and at least one liquid other than it, in which the cellulosic material is not soluble or less soluble than in the ionic liquid.

In the context of the present application, ionic liquids refer to organic salts which are already liquid at temperatures below 180 ^° C. Preferably, the ionic liquids have a melting point of less than 180 ⁰ C. Further, preferably the melting point is in the range from -50 ⁰ C to 150 ⁰ C, more preferably in the range from -20 ⁰ C to 120 ⁰ C and more preferably below 100 ⁰ C.

Ionic liquids already in liquid state at room temperature are described, for example, by KN Marsh et al., Fluid Phase Equilibria 219 (2004), 93-98 and JG Huddieston et al., Green Chemistry 2001, 3, 156-164. wrote.

Cations and anions are present in the ionic liquid. In this case, within the ionic liquid from the cation, a proton or an alkyl radical can be transferred to the anion, resulting in two neutral molecules. In the ionic liquid used according to the invention, therefore, there can be an equilibrium of anions, cations and neutral molecules formed therefrom.

The ionic liquids used according to the invention have polyatomic, d. H. polyatomic anions, with two or more than two atoms on.

In the context of the present invention, the term "alkyl" includes straight-chain or branched alkyl. It is preferably straight-chain or branched C 1 -C 30 -alkyl, in particular C 1 -C -alkyl, and very particularly preferably C 1 -C 12 -alkyl. Examples of alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 1-methyl-butyl, tert-pentyl, neopentyl, n-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, n-heptyl, n-octyl, 1-methylheptyl, 2-ethylhexyl, 2,4, 4-trimethyl-pentyl, 1,1,3,3-tetramethylbutyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n- Heptadecyl, n-octadecyl and n-eicosyl.

The term alkyl also includes alkyl radicals whose carbon chain is replaced by one or more nonadjacent heteroatoms or heteroatom-containing groups which are preferably selected from -O-, -S-, -NR ^a -, -PR ^a -, -SiR ^a R ^aa and / or -SO2- can be interrupted. R ^a is preferably hydrogen, alkyl, cycloalkyl, hetero cycloalkyl, aryl or hetaryl. R ^aa is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, or aryl.

Examples of alkyl radicals whose carbon chains may be interrupted by one or two nonadjacent heteroatoms -O- are the following:

Methoxymethyl, diethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, diethoxyethyl, 2-butoxyethyl, 2-octyloxyethyl, 2-methoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 2-isopropoxyethyl, 2-butoxypropyl, 3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-propoxybutyl, 6-methoxyhexyl, 3,6-dioxa-heptyl (5-methoxy-3-oxa-pentyl), 3,6-dioxa-octyl (7-methoxy 4-oxa-heptyl), 4,8-dioxa-nonyl (7-methoxy-4-oxa-heptyl), 3,7-dioxa-octyl, 3,7-dioxa-nonyl, 4,7-dioxa-octyl , 4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 9-ethoxy-5-oxa-nonyl.

Examples of alkyl radicals whose carbon chains may be interrupted by three or more than three nonadjacent heteroatoms -O- are also oligo- and polyoxyalkylenes, ie compounds having repeating units which are preferably selected from (CH ₂ CH ₂ O) χi, (CH (CH ₃ ) CH ₂ O) χ2 and ((CH ₂ ) 4θ) _x3 , where x1, x2 and x3 independently of one another are an integer from 3 to 100, preferably from 3 to 80. The sum of x1, x2 and x3 is an integer from 3 to 300, especially 3 to 100. In polyoxyalkylenes having two or three different repeating units, the order is arbitrary, ie it may be random, alternating or block-shaped Repeat units act. Examples of these are 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 4,8,12-trioxatridecyl (1-methoxy-4,8-dioxa-undecyl), 4 , 8.12-Trioxatetradecyl,

14-methoxy-5,10-dioxa-tetradecyl, 5,10,15-trioxaheptadecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12-tetraoxatetradecyl, 4,8,12,16-tetraoxaheptadecyl ( 15-methoxy-4,8,12-trioxapentadecyl), 4,8,12,16-tetraoxa-octadecyl and the like.

Examples of alkyl radicals whose carbon chains by one or more, for. B. 1, 2, 3, 4 or more than 4, non-adjacent heteroatoms -S- may be interrupted, are the following:

Butylthiomethyl, 2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-butylthio-ethyl, 2-dodecylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-propylthiopropyl,

3-butylthiopropyl, 4-methylthiobutyl, 4-ethylthiobutyl, 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithio-octyl, 4,8-dithia-nonyl, 3,7-dithio-octyl, 3, 7-di-thia-nonyl, 2- and 4-butylthiobutyl, 4,8-dithia-decyl, 3,6,9-trithia-decyl, 3,6,9-trithia-undecyl, 3,6,9-trithia dodecyl, 3,6,9,12-tetrathia-tridecyl and 3,6,9,12-tetrathia-tetradecyl.

Examples of alkyl radicals whose carbon chains are interrupted by one or two non-adjacent heteroatom-containing groups -NR ^a - are the following: 2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 3-methylaminopropyl, 2- and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and 4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl, 6-methylaminohexyl, 6- Dimethylaminohexyl, 6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl and 3,6-dimethyl-3,6-diazaoctyl.

Examples of alkyl radicals whose carbon chains may be interrupted by three or more than three non-adjacent heteroatom-containing groups -NR ^a - are also oligo- and polyalkyleneimines. The comments made above for the polyoxyalkylenes apply analogously to polyalkyleneimines, wherein the oxygen atom is replaced in each case by a group NR ^a , in which R ^{a is} preferably hydrogen or C 1 -C ₄ -alkyl. Examples of these are 9-methyl-3,6,9-triazadecyl, 3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl, 3,6,9-trimethyl-3,6 , 9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyl, 3,6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl, and the like.

Examples of alkyl radicals whose carbon chains by one or more, for. B. 1 or 2 non-adjacent groups -SO2- are interrupted, are 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-Butylsulfonylethyl, 2-methylsulfonylpropyl, 3-methylsulfonylpropyl, 2-ethylsulfonyl propyl, 3rd Ethylsulfonylpropyl, 2-propylsulfonylpropyl, 3-propylsulfonylpropyl, 2-butylsulfonylpropyl, 3-butylsulfonylpropyl, 2-methylsulfonylbutyl, 4-methylsulfonylbutyl, 2-ethylsulfonylbutyl, 4-ethylsulfonylbutyl, 2-propylsulfonylbutyl, 4-propylsulfonylbutyl and 4-butylsulfonylbutyl.

The term alkyl also includes substituted alkyl radicals. Substituted alkyl groups may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the length of the alkyl chain. These are preferably selected independently from among cycloalkyl, cycloalkyloxy, polycyclyl, polycycloxy, heterocycloalkyl, aryl, aryloxy, arylthio, hetaryl, halogen, hydroxy, SH, = 0, = S, = NR ^a , COOH, carboxylate, SO ₃ H, sulfonate , NE ¹ E ² , nitro and cyano, wherein E ¹ and E ^{2 are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Cycloalkyl, cycloalkyloxy, polycycloalkyl, polycycloalkyloxy, heterocycloalkyl, aryl and hetaryl substituents of the alkyl groups may themselves be unsubstituted or substituted; suitable substituents are those mentioned below for these groups.

The above comments on alkyl also apply in principle to the alkyl moieties in alkoxy, alkylamino, dialkylamino, alkylthio (alkylsulfanyl), alkylsulfinyl, alkylsulfonyl, etc. Suitable substituted alkyl radicals are the following:

Alkyl substituted by carboxy, such as. Carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 7-carboxyheptyl, 8-carboxyctyl, 9-carboxynonyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxytetradecyl;

Alkyl which is substituted by SO3H, such as. Sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 7-sulfoheptyl, 8-sulfooctyl, 9-sulfononyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl;

Alkyl which is substituted by carboxylate, such as. Alkoxycarbonylalkyl, e.g. Methoxycarbonylmethyl, ethoxycarbonylmethyl, n-butoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-methoxycarbonylpropyl, 2-ethoxycarbonylpropyl, 2- (n-butoxycarbonyl) propyl, 2- (4-n-butoxycarbonyl) propyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 3- (n-butoxycarbonyl) propyl, 3- (4-n-butoxycarbonyl) propyl, aminocarbonylalkyl, e.g. Aminocarbonylmethyl, aminocarbonylethyl, aminocarbonylpropyl and the like, alkylaminocarbonylalkyl such as methylaminocarbonylmethyl, methylaminocarbonylethyl, ethylcarbonylmethyl, ethylcarbonylethyl and the like, or dialkylaminocarbonylalkyl such as dimethylaminocarbonylmethyl, dimethylaminocarbonylethyl, dimethylcarbonylpropyl, diethylaminocarbonylmethyl, diethylaminocarbonylethyl, diethylcarbonylpropyl and the like.

Alkyl substituted by hydroxy, such as. 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 2-hydroxy-2,2-dimethylethyl,

5-hydroxy-3-oxa-pentyl, 6-hydroxyhexyl, 7-hydroxy-4-oxa-heptyl, 8-hydroxy-4-oxo-octyl, 8-hydroxy-3,6-dioxo-octyl, 9-hydroxy 5-oxa-nonyl, 1 1-hydroxy-4,8-dioxa- undecyl, 11-hydroxy-3,6,9-trioxa-undecyl, 14-hydroxy-5,10-dioxa-tetradecyl,

15-hydroxy-4,8,12-trioxa-pentadecyl and the like.

Alkyl which is substituted by amino, such as. 2-aminoethyl, 2-aminopropyl,

3-aminopropyl, 4-aminobutyl, 6-aminohexyl and the like.

Alkyl which is substituted by cyano, such as. 2-cyanoethyl, 3-cyanopropyl, 3-cyanobutyl and 4-cyanobutyl;

Alkyl which is substituted by halogen, as defined below, wherein in the alkyl group, the hydrogen atoms may be partially or completely replaced by halogen atoms, such as Ci-cis-fluoroalkyl, z. Trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl and the like, Ci-Cis-chloroalkyl, z. Chloromethyl, dichloromethyl, trichloromethyl, 2-chloroethyl, 2- and 3-chloropropyl, 2-, 3- and 4-chlorobutyl, 1, 1-dimethyl-2-chloroethyl and the like, Ci-Ci8-bromoalkyl, e.g. Bromoethyl, 2-bromoethyl, 2- and 3-bromopropyl and 2-, 3- and 4-bromobutyl and the like

Alkyl which is substituted by nitro, such as. 2-nitroethyl, 2- and 3-nitropropyl and 2-, 3- and 4-nitrobutyl and the like.

Alkyl which is substituted by amino, such as. 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl and the like.

Alkyl substituted by cycloalkyl, such as. Cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl and the like.

Alkyl which is substituted by = 0 (oxo group), such as. 2-oxopropyl, 2-oxobutyl, 3-oxobutyl, 1-methyl-2-oxopropyl, 2-oxopentyl, 3-oxopentyl, 1-methyl-2-oxobutyl, 1-methyl-3-oxobutyl, 2-oxohexyl, 3-oxohexyl, 4-oxohexyl, 2-oxoheptyl, 3-oxoheptyl, 4-oxoheptyl, 4-oxoheptyl and the like.

Alkyl which is substituted by = S (thioxo), such as. For example, 2-thioxopropyl,

2-thioxobutyl, 3-thioxobutyl, 1-methyl-2-thioxopropyl, 2-thioxopentyl, 3-thioxopentyl, 1-methyl-2-thioxobutyl, 1-methyl-3-thioxobutyl, 2-thioxohexyl, 3-thioxohexyl, 4- Thioxohexyl, 2-thioxoheptyl, 3-thioxoheptyl, 4-thioxoheptyl, 4-thioxoheptyl and the like.

Alkyl, which is substituted by = NR ^a -, preferably those in which R ^{a is} hydrogen or Ci-C4-alkyl, such as. 2-iminopropyl, 2-iminobutyl, 3-iminobutyl, 1-methyl-2-iminopropyl, 2-iminopentyl, 3-iminopentyl, 1-methyl-2-iminobutyl, 1-methyl-3-imino-butyl, 2- isohexyl, 3-iminohexyl, 4-iminohexyl, 2-iminoheptyl, 3-iminoheptyl, 4-iminoheptyl, 4-iminoheptyl, 2-methyliminopropyl, 2-methyliminobutyl, 3-methyliminobutyl, 1-methyl-2-methyliminopropyl, 2-methyliminopentyl, 3-methyliminopentyl, 1-methyl-2-methyliminobutyl, 1-methyl-3-methyliminobutyl, 2-methyliminohexyl, 3-methyliminohexyl, 4-methyliminohexyl, 2-methyliminoheptyl, 3-methyliminoheptyl, 4-methyliminoheptyl, 4-methyliminoheptyl, 2- Ethyliminopropyl, 2-ethyliminobutyl, 3-ethyliminobutyl, 1-methyl-2-ethyliminopropyl, 2-ethyliminopentyl, 3-ethyliminopentyl, 1-methyl-2-ethyliminobutyl, 1-methyl-3-ethyliminobutyl, 2-ethyliminohexyl, 3-ethyliminohexyl, 4-ethyliminohexyl, 2-ethyliminoheptyl, 3-ethyliminoheptyl, 4-ethyliminoheptyl, 4-ethyliminoheptyl, 2-propyliminopropyl, 2-propyliminobutyl, 3-propyliminobutyl, 1-methyl-2-propyliminopropyl, 2-propyliminopentyl, 3-propyliminopentyl, 1-methyl-2-propyliminobutyl, 1-methyl-3-propyliminobutyl, 2-propyliminohexyl, 3-propyliminohexyl, 4-propyliminohexyl, 2-propyliminoheptyl, 3-propyliminoheptyl, 4-propyliminoheptyl, 4-propyliminoheptyl and the like.

Alkoxy is an alkyl group bonded via an oxygen atom. Examples of alkoxy are: methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1, 1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 , 1-Dimethylpropoxy, 1, 2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy , 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2,2-trimethylpropoxy, 1 -Ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy, hexoxy and 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 is} hydrogen or Ci C ₄ alkyl, preferably hydrogen, methyl or ethyl and n is 0 to 10, preferably 0 to 3.

Alkylthio (alkylsulfanyl) is an alkyl group bonded via a sulfur atom. Examples of alkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio and hexylthio.

Alkylsulfinyl for a via an S (= O) group bonded alkyl group.

Alkylsulfinyl is an alkyl group bonded via an S (= O) ₂ group.

Aryl-substituted alkyl radicals ("arylalkyl") have at least one, as defined below, unsubstituted or substituted aryl group. Suitable substituents on the aryl group are the following. In this case, the alkyl group in "arylalkyl" may bear at least one further substituent as defined above and / or by one or more nonadjacent heteroatoms or heteroatom-containing groups which are selected from -O-, -S-, -NR ^a - , and / or SO ₂ - be under- broke. Arylalkyl is preferably phenyl-Ci-Cio-alkyl, particularly preferably phenyl-Ci-C ₄ -alkyl, z. For benzyl, 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1 -yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl , 1- (phen-meth) -eth-1-yl, 1- (phen-methyl) -1- (methyl) -eth-1-yl or - (phen-methyl) -1- (methyl) -prop-1-yl; preferably for benzyl and 2-phenethyl.

The term "alkenyl" in the context of the present invention comprises straight-chain and branched alkenyl groups which, depending on the chain length, may carry one or more double bonds (eg 1, 2, 3, 4 or more than 4). Preference is given to C ₂ -Cis, particularly preferably C ₂ -C ₂ -alkenyl groups. The term "alkenyl" also includes substituted alkenyl groups containing one or more (e.g., 1, 2, 3, 4, 5, or more than 5) substituents can carry. Suitable substituents are, for. B. selected under = 0, = S, = NR ^a , cycloalkyl, cycloalkyloxy, polycyclyl, polycycloxy, heterocycloalkyl, aryl, aryloxy, arylthio, hetaryl, halogen, hydroxy, SH, COOH, carboxylate, SO ₃ H, sulfonate, Alkylsulfinyl, alkylsulfonyl, NE ³ E ⁴ , nitro and cyano, wherein E ³ and E ^{4 are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

The term "alkenyl" also includes alkenyl radicals whose carbon chain may be interrupted by one or more nonadjacent heteroatoms or heteroatom-containing groups, which are preferably selected from -O-, -S-, -NR ^a - and / or -SO 2 -.

Alkenyl is then for example ethenyl (vinyl), 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,

Penta-1,3-dien-1-yl, hexa-1, 4-dien-1-yl, hexa-1, 4-dien-3-yl, hexa-1,4-dien-6-yl, hexa 1, 5-dien-1-yl, hexa-1, 5-dien-3-yl, hexa-1, 5-dien-4-yl, hepta-1, 4-dien-1-yl, hepta-1, 4-dien-3-yl, hepta-1, 4-dien-6-yl, hepta-1, 4-dien-7-yl, hepta-1, 5-dien-1-yl, hepta-1, 5 dien-3-yl, hepta-1, 5-dien-4-yl, hepta-1, 5-dien-7-yl, hepta-1, 6-dien-1-yl, hepta-1, 6-diene 3-yl, hepta-1, 6-dien-4-yl, hepta-1, 6-dien-5-yl, hepta-1, 6-dien-2-yl, octa-1, 4-diene-1 yl, octa-1, 4-dien-2-yl, octa-1, 4-dien-3-yl, octa-1, 4-dien-6-yl, octa-1, 4-dien-7-yl, Octa-1, 5-dien-1-yl, octa-1, 5-dien-3-yl, octa-1, 5-dien-4-yl, octa-1, 5-dien-7-yl, octa-1-yl 1, 6-dien-1-yl, octa-1, 6-dien-3-yl, octa-1, 6-dien-4-yl, octa-1, 6-dien-5-yl, octa-1, 6-dien-2-yl, deca-1, 4-dienyl, deca-1, 5-dienyl, deca-1, 6-dienyl, deca-1, 7-dienyl, deca-1, 8-dienyl, deca 2,5-dienyl, deca-2,6-dienyl, deca-2,7-dienyl, deca-2,8-dienyl and the like.

The term "cycloalkyl" in the context of the present invention comprises unsubstituted as well as substituted monocyclic saturated hydrocarbon groups having generally 3 to 12 carbon ring members, preferably C3-C12-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentyl , Cyclodecyl, cycloundecyl or cyclododecyl, in particular C5-Ci2-cycloalkyl. Suitable substituents are as a rule selected for alkyl, the substituents mentioned above for the alkyl groups, alkoxy and also alkylthio. Substituted cycloalkyl groups may have one or more (for example 1, 2, 3, 4, 5 or more than 5) substituents, where in the case of halogen the cycloalkyl radical is partially or completely substituted by halogen.

Examples of cycloalkyl groups are cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, chloropentyl, dichloropentyl, dimethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3 and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3 and 4-tert-butylcyclohexyl, chlorhexyl, dimethylcyclohexyl, diethylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butoxycyclohexyl, methylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, cycloheptyl, 2-, 3- and 4-methylcycloheptyl, 2-, 3- and 4 Ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and 4-tert-butylcycloheptyl, cyclooctyl, 2-, 3- , 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl, 3-, 4- and 5-propylcyclooctyl, partially fluorinated cycloalkyl and perfluorinated cycloalkyl of the formula C _n F 2 ( _n -a) - (ib ) H2a-b with n = 5 to 12, 0 ≤ a ≤ n and b = 0 or 1.

Cycloalkyloxy is an oxygen-bonded cycloalkyl group as defined above.

The term "cycloalkenyl" includes unsubstituted and substituted, mono- or di-unsaturated hydrocarbon groups having 3 to 5 to 8 to 12, preferably 5 to 12 carbon ring members such as cyclopent-1-en-1-yl, cyclopent-2-en-1 -yl, cyclopent-3-en-1-yl, cyclohex-1-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl, cyclohexa-2,5-diene -1-yl and the like. Suitable substituents are those previously mentioned for cycloalkyl.

Cycloalkenyloxy is an oxygen-bonded cycloalkenyl group as defined above.

The term "polycyclyl" in the context of the present invention in the broadest sense compounds containing at least two rings, regardless of how these rings are linked. These may be carbocyclic and / or heterocyclic rings. The rings can be saturated or unsaturated. The rings can be linked via single or double bonds ("polynuclear compounds"), linked by annulation ("fused ring systems") or bridged ("bridged ring systems", "cage compounds"). Preferred polycyclic compounds are bridged ring systems and fused ring systems. Condensed ring systems may be fused (fused) aromatic, hydroaromatic and cyclic compounds by annulation. Condensed ring systems consist of two, three or more than three rings. Depending on the type of linkage, in fused ring systems a distinction is made between ortho-annulation, ie, each ring has one edge or two atoms in common with each adjacent ring, and a peri-annulation in which one carbon atom belongs to more than two rings. Preferred among the fused ring systems are ortho-fused ring systems. Bridged ring systems in the context of the present invention include those which do not belong to the polynuclear ring systems and not to the fused ring systems and in which at least two ring atoms belong to at least two different rings. In the bridged ring systems, Depending on the number of ring-opening reactions which are formally required to arrive at an open-chain compound, one distinguishes bi-, tri-, tetracyclo-compounds, etc., which consist of two, three, four, etc. rings. The term "bicycloalkyl" encompasses bicyclic hydrocarbon radicals having preferably 5 to 10 C atoms, such as bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [2.2.1] hept-7-yl, bicyclo [2.2.2] oct-1-yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.3.0] octyl, bicyclo [4.4.0] decyl and the like. The term "bicycloalkenyl" includes monounsaturated, bicyclic hydrocarbon radicals preferably having 5 to 10 carbon atoms, such as bicyclo [2.2.1] hept-2-en-1-yl.

The term "aryl" in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted. Aryl is usually for hydrocarbon radicals having 6 to 10, to 14, to 18, preferably 6 to 10 carbon ring members. Aryl is preferably unsubstituted or substituted phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and particularly preferably phenyl or naphthyl. Substituted aryls may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the number and size of their ring systems. These are preferably selected independently from among alkyl, alkoxy, cycloalkyl, cycloalkyloxy, heterocycloalkyl, aryl, aryloxy, arylthio, hetaryl, halogen, hydroxy, SH, alkylthio, alkylsulfinyl, alkylsulfonyl, COOH, carboxylate, SO ₃ H, sulfonate, NE ⁵ E ⁶ , nitro and cyano, wherein E ⁵ and E ⁶ independently of one another represent hydrogen, alkyl, cycloalkyl, cycloalkyloxy, polycyclylyl, polycycloxy, heterocycloalkyl, aryl, aryloxy or hetaryl. Aryl is particularly preferably phenyl, which in the case of a substitution can generally carry 1, 2, 3, 4 or 5, preferably 1, 2 or 3, substituents.

Aryl which carries one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6- Trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl , 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl, 2,4,6-tri-sec-butylphenyl, 2-, 3 and 4-tert-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl and 2- , 3, 4-dodecylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2 , 4-, 2,5-, 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 2,5-, 3, 5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl, 2-, 3- and 4-butoxyphenyl, 2-, 3-, 4-hexyloxyphenyl; 2-, 3-, 4-chlorophenyl, 2,4-, 2,5-, 3,5- and 2,6-dichlorophenyl, trichlorophenyl, 2-, 3-, 4-fluorophenyl, 2,4-, 2,5-, 3,5- and 2,6-difluorophenyl, trifluorophenyl, such as. 2,4,6-trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, 2-, 3- and 4-cyanophenyl; 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl; 4-dimethylaminophenyl; 4-acetylphenyl; Methoxyethylphenyl, ethoxymethylphenyl; Methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl; methylnaphthyl; Isopropylnaphthyl or ethoxynaphthyl. Examples of substituted aryl wherein two substituents attached to adjacent carbon atoms of the aryl ring form a fused ring or fused ring system are indenyl and fluorenyl.

The term "aryloxy" in the context of the present invention stands for aryl bound via an oxygen atom.

The term "arylthio" in the context of the present invention stands for aryl bound via a sulfur atom.

The term "heterocycloalkyl" in the context of the present invention comprises non-aromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms by heteroatoms selected from oxygen , Nitrogen, sulfur and a group -NR ^a - are replaced and which is unsubstituted or substituted by one or more, for example, 1, 2, 3, 4, 5 or 6, C 1 -C 6 -alkyl groups. Examples of such heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothienyl, dihydrothienyl, tetrahydrofuranyl, dihydrofuranyl, Tetrahydropyranyl, 1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl called. Nitrogen-containing heterocycloalkyl can in principle be bound both via a carbon atom and via a nitrogen atom.

The term "heteroaryl (hetaryl)" in the context of the present invention comprises unsubstituted or substituted, heteroaromatic, mononuclear or polynuclear groups having generally 5 to 14 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms one, two, three or four heteroatoms selected from O, N, -NR ^a and S are substituted, such as furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzofuranyl, benzthiazolyl, benzimidazolyl, pyridyl, quinolinyl, acridinyl , Pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1, 2,3-triazolyl, 1, 3,4-triazolyl and carbazolyl, these heterocycloaromatic groups in the case of a substitution in im Generally 1, 2 or 3 substituents. The substituents are as a rule selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxyl, carboxyl, halogen and cyano. 5- to 7-membered nitrogen-containing heterocycloalkyl or heteroaryl radicals which optionally contain further heteroatoms are, for example, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, pyridinyl, pyridazinyl, pyrimidinyl, Pyrazinyl, triazinyl, piperidinyl, piperazinyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, indolyl, quinolinyl, isoquinolinyl or quinaldinyl, which may be unsubstituted or substituted as mentioned above.

Halogen is fluorine, chlorine, bromine or iodine.

Carboxylate and sulfonate in the context of this invention preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic ester or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function. These include z. As the esters with Ci-C4-alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.

The term "acyl" in the context of the present invention represents alkanoyl, hetaroyl or aroyl groups having generally 1 to 11, preferably 2 to 8, carbon atoms, for example the formyl, acetyl, propanoyl, butanoyl, pentanoyl , Hexanoyl, heptanoyl, 2-ethylhexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.

The radicals E ¹ and E ² , E ³ and E ⁴ , E ⁵ and E ⁶ are independently selected from hydrogen, alkyl, cycloalkyl and aryl. The groups NE ¹ E ² , NE ³ E ⁴ and NE ⁵ E ⁶ are preferably N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n -butylamino, N, N-di-tert-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.

In principle, all ionic liquids based on polyatomic anions are suitable for use in the process according to the invention.

Preferred ionic liquids are

(A) Salts of the general formula (I)

[A]; [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 polyatomic, mono-, di-, tri- or tetravalent anion or mixtures of these anions; (B) mixed salts of the general formulas (II)

[A ¹ ] ⁺ [A ² ] ⁺ [Y] - (I La), where n = 2, [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] - (II.b. ), where n = 3,

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

wherein [A ¹ J ⁺ , [A ² ] ⁺ , [A ³ J ⁺ and [A ⁴ J ^{+ 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] - (II La), where n = 4,

[A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] "- (III.b), where n = 4, [A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [M ³ ] ⁺ [Y] "- (III.c), where n = 4,

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

[A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] "- (III.e), where n = 3,

[A ¹ ] ⁺ [M ¹ ] ⁺ [Y] "- (III.f), where n = 2,

[A ¹ ] ⁺ [A ² ] ⁺ [M ⁴ ] ²⁺ [Y] "- (II Lg), where n = 4, [A ¹ ] ⁺ [M ¹ ] ⁺ [M ⁴ ] ²⁺ [Y ] "- (lll.h), where n = 4,

[A ¹ J ⁺ [M ⁵ J ³⁺ [Y] "- (II Li), where n = 4,

[A ¹ ] ⁺ [M ⁴ ] ²⁺ [Y] "- (II Lj), where n = 3, and

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

Preferred are salts of groups A and B, more preferably of group A.

The metal cations [M ¹ ] ⁺ , [M ² J ⁺ , [M ³ J ⁺ , [M ⁴ J ²⁺ and [M ⁵ J ³⁺ ] mentioned in formulas (III.a) to (III.j) are They are generally metal cations of the 1st, 2nd, 6th, 7th, 8th, 9th, 10th, 11th, 12th, 13th and 14th 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⁺ .

Suitable compounds which are suitable for forming the cation [A] ⁺ of ionic liquids are, for. B. in DE 102 02 838 A1. These compounds preferably contain at least one heteroatom, such as. B. 1 to 10 heteroatoms, which are preferably selected from nitrogen, oxygen, phosphorus and sulfur atoms. Preference is given to compounds which have at least one nitrogen atom and, if appropriate, at least one further heteroatom other than nitrogen. contain atom. Preference is given to compounds which contain at least one nitrogen atom, particularly preferably 1 to 10 nitrogen atoms, in particular 1 to 5 nitrogen atoms, very particularly preferably 1 to 3 nitrogen atoms and especially 1 or 2 nitrogen atoms. The latter nitrogen compounds may contain other heteroatoms such as oxygen, sulfur or phosphorus atoms.

The nitrogen atom is z. B. a suitable carrier of the positive charge in the cation of the ionic liquid. 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 protonation of the nitrogen atom. Depending on the protonation 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 resulting Metallha- logenids, via an ion exchanger or by displacement of the halide ion by a strong acid (to release the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 112, p. 3926-3945 and the literature cited therein.

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 optionally an oxygen or sulfur atom, particular preference is given to those compounds which contain at least one five- to six-membered heterocycle, which has one, two or three nitrogen atoms and one sulfur 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 molar mass of less than 1000 g / mol, very particularly preferably less than 600 g / mol and in particular less than 400 g / mol.

Preferred cations are selected from the compounds of the formulas (IV.a) to (IV.z),

(IV.a) (IV.b) (IV.c)

(IV.d) (IV.e)

(iv.g) (iv.g ¹ )

(IV.i) (iv.j)

(IV.m) (IV.m¹) (IV.n)

(IV.m) (IV.m ¹ ) (IV.n)

(IV.n ¹ ) (IV.o) (IV.o ¹ )

(IV.p) (IV.q) (IV.q ')

(IV.q ") (IV.r) (IV.r ')

(IV.r ") (IV.s) (IV.t)

(IV.u) (IV.v) (IV.w)

(IV.x.1) (IV.x.2)

(IV.y) (IV.z)

and oligomers containing these structures, wherein

R is hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, polycyclyl, heterocycloalkyl, aryl or heteroaryl;

Radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ which are bonded to a ring carbon atom, independently of one another, represent hydrogen, a sulfo group, COOH, carboxylate, sulfonate , Acyl, alkoxycarbonyl, cyano, halogen, hydroxyl, SH, nitro,

NE ¹ E ² , alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, polycyclyl, polycycloxy, heterocycloalkyl, aryl, aryloxy or heteroaryl, where E ¹ and E ² independently of one another represent hydrogen , Alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,

Radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , which are bonded to a ring heteroatom, for hydrogen, SO ₃ H, NE ¹ E ² , alkyl, alkoxy , Alkenyl, cycloalkyl, cycloalkenyl, polycyclyl, heterocycloalkyl, aryl or heteroaryl, where E ¹ and E ² independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or

Hetaryl stand, or

two adjacent radicals R ¹ to R ⁹ together with the ring atoms to which they are attached may stand for at least one fused, saturated, unsaturated or aromatic ring or a ring system having 1 to 30 carbon atoms, the ring or the ring system 1 to 5 may have non-adjacent heteroatoms or heteroatom-containing groups and wherein the ring or the ring system may be unsubstituted or substituted,

where two geminal radicals R ¹ to R ^{9 can} also together stand for = 0, = S or = NR ^b , where R ^{b is} hydrogen, alkyl, cycloalkyl, aryl or heteroaryl,

where in the compounds of the formula (IV.x.1) R ¹ and R ³ or R ³ and R ^{5 may} also together be the bond moiety of a double bond between the ring atoms which carry these radicals,

B in the compounds of the formulas (IV.x.1) and (IV.x.2) together with the CN group to which it is attached, a 4- to 8-membered, saturated or forms unsaturated or aromatic cycle which is optionally substituted and / or which may optionally have further heteroatoms or heteroatom-containing groups and / or may comprise further fused saturated, unsaturated or aromatic carbocycles or heterocycles.

With regard to the general meaning of the abovementioned radicals carboxylate, sulfonate, acyl, alkoxycarbonyl, halogen, NE ¹ E ² , alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, polycyclyl, polycycloxy , Heterocycloalkyl, aryl, aryloxy or heteroaryl is referred to the introductory statements made in full. Radicals R ¹ to R ⁹ which are bonded to a carbon atom in the abovementioned formulas (IV) and have a heteroatom or a heteroatom-containing group can also be bonded to the carbon atom directly via a heteroatom.

Two adjacent radicals R ¹ to R ^9, together with the ring atoms to which they are attached, form at least one fused, saturated, unsaturated or aromatic ring or a ring system having from 1 to 30 carbon atoms, the ring or the ring system not being adjacent to 1 to 5 Heteroatoms or heteroatom-containing groups and wherein the ring or the ring system may be unsubstituted or substituted, these radicals may together as fused building blocks 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-az-1, 4-buta-1, 3-dienylene or 2-aza-1,4-buta-1,3-dienylene.

The radical R preferably stands for

unsubstituted C 1 to C 18 alkyl, 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 and 1-octadecyl;

one to several times with hydroxy, halogen, phenyl, cyano, Ci-Cβ-alkoxycarbonyl and / or SO3H substituted Ci-Cis-alkyl, especially hydroxy-Ci-Cis-alkyl, such as. 2-hydroxyethyl or 6-hydroxyhexyl; Phenyl-Ci-cis-alkyl, such as. Benzyl,

3-phenylpropyl; Cyano-Ci-Cis-alkyl, such as. For example, 2-cyanoethyl; Ci-Cβ-alkoxy-Ci-Cis alkyl, such as. B. 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl or 2- (n-Butoxy-carbonyl) -ethyl; C 1 -C 6 -fluoroalkyl, such as trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl; Sulfo-Ci-cis alkyl, such as. For example, 3-sulfopropyl;

Hydroxyethyloxyalkyl, radicals of oligo- and polyalkylene glycols such as polyethylene glycols and polypropylene glycols and their oligomers having 2 to 100 units and a hydrogen or a C 1 -C 5 -alkyl as an end group, such as R ^A O- (CH R ^B -CH ₂ -O ) n-CH R ^B -CH ₂ - with R ^A and R ^{B is} preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxa-butyl,

3-oxa-pentyl, 3,6-dioxa-heptyl, 3,6-dioxa-octyl, 3,6,9-trioxa-decyl, 3,6,9-trioxa-undecyl, 3,6,9,12- Tetraoxa-tridecyl and 3,6,9,12-tetraoxa-tetradecyl; and

C ₂ -C 6 alkenyl, such as vinyl or propenyl.

The radical R particularly preferably represents linear 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, most preferably methyl, ethyl, 1-butyl and 1-octyl and CH ₃ O- (CH ₂ CH ₂ O) _n -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - with m equal to 0 to 3.

The radicals R ¹ to R ⁹ are preferably each independently

Hydrogen;

Halogen;

a functional group selected from hydroxy, alkoxy, alkylthio, carboxyl, -COOH, sulfonate, cyano, acyl, alkoxycarbonyl, NE ¹ E ² and nitro, wherein E ¹ and E ^{2 are} as defined above;

C 1 -C 18 -alkyl which is unsubstituted or, as defined above, is substituted and / or, as defined above, may be interrupted by at least one heteroatom or a heteroatom-containing group;

C ₂ -C -alkenyl which is unsubstituted or, as defined above, is substituted and / or, as defined above, may be interrupted by at least one heteroatom;

- Cβ-Cio-aryl, which is unsubstituted or, as defined above, is substituted; C 5 -C 12 -cycloalkyl which is unsubstituted or substituted as defined above;

Polycyclyl which is unsubstituted or substituted as defined above;

C 5 -C 12 cycloalkenyl which is unsubstituted or substituted as defined above;

Heterocycloalkyl having 5 or 6 ring atoms, wherein the ring next to carbon ring members 1, 2 or 3 heteroatom or heteroatom-containing groups which are selected from oxygen, nitrogen, sulfur and NR ^a , and which is unsubstituted or, as defined above, is substituted ;

Heteroaryl having 5 to 10 ring atoms, wherein the ring in addition to carbon ring having 1, 2 or 3 heteroatoms or heteroatom-containing groups which are selected from oxygen, nitrogen, sulfur and NR ^a , and which is unsubstituted or, as defined above, is substituted ,

It is also preferred that two adjacent radicals R ¹ to R ⁹ together with the ring atoms to which they are attached may stand for at least one fused, saturated, unsaturated or aromatic ring or a ring system having 1 to 12 carbon atoms, said Ring or the ring system may have 1 to 5 non-adjacent heteroatoms or heteroatom-containing groups, which are preferably selected from oxygen, nitrogen, sulfur and NR ^a , and wherein the ring or the ring system is unsubstituted or may be substituted, wherein the substituents are preferably independently are selected from alkoxy, cycloalkyl, cycloalkoxy, polycyclyl, polycycloxy, heterocycloalkyl, aryl, aryloxy, arylthio, heteroaryl halogen, hydroxy, SH, = O, = S, = NR ^a , COOH, carboxylate, -SO ₃ H, SuI - Fonat, NE ¹ E ² , nitro and cyano, wherein E ¹ and E ^{2 are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl n.

When R ¹ to R ^{9 are} alkoxy, R ¹ to R ^{9 are} preferably methoxy or ethoxy 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 0 to 3.

When R ¹ to R ^{9 are} acyl, R ¹ to R ^{9 are} preferably formyl and C 1 -C 4 -alkylcarbonyl, in particular formyl or acetyl.

If R ¹ to R ^{9 are} C ¹ -C 6 -alkyl, then R ¹ to R ^{9 are} preferably unsubstituted C ¹ -C 18 -alkyl, 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-9-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-trimethyl-pentyl, 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;

C 1 -C 18 -haloalkyl, especially C 1 -C 18 -fluoroalkyl, for example trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonofluoroisobutyl, undecylfluoropentyl, undecylisopentyl, C 6 F 13, CsFi ₇ , C 10 F 21, C 12 F 25, especially Cis-chloroalkyl such as chloromethyl, 2-chloroethyl, trichloromethyl, 1, 1-dimethyl-2-chloroethyl;

Amino-Ci-Ci8-alkyl, such as 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, Ci-C6-alkylamino-Ci-Ci8-alkyl, such as 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl; Di- (C 1 -C 6 -alkyl) C 1 -C 4 -alkyl, such as 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, cyano-C 1 -C 18 -alkyl, such as 2-cyanoethyl, 2-cyanopropyl, C 1 -C 10 -alkoxy-C 1 -C 18 -alkyl, such as methoxymethyl, 2-methoxyethyl, 2-methoxypropyl,

3-methoxypropyl, 2-methoxyisopropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, 2-isopropoxyethyl, 2-butoxyethyl, 2-butoxypropyl, 2- Octyloxyethyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 7-methoxy-4-oxa-heptyl, 1-methoxy-4,8-dioxa-undecyl, 9-methoxy 5-oxa-nonyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl , 7-ethoxy-4-oxa-heptyl, 1-ethoxy-4,8-dioxa-undecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl, 15-methoxy 4,8,12-trioxa-pentadecyl, 1-methoxy-3,6,9-trioxa-undecyl, 11-ethoxy-3,6,9-trioxa-undecyl, 15-ethoxy-4,8,12-trioxa pentadecyl;

Di (C 1 -C 10 -alkoxy-C 1 -C 18 -alkyl), such as diethoxymethyl or diethoxyethyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl, such as 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, di- (C 1 -C 6 -alkoxycarbonyl) -Ci-C 18 -alkyl, such as 1, 2-di- (methoxycarbonyl) -ethyl, hydroxy-C 1 -C 18 -alkyl, such as 2- Hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,

4-hydroxybutyl, 6-hydroxyhexyl, 2-hydroxy-2,2-dimethylethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxo-octyl, 11-hydroxy-3,6,9- trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 1-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl , 14-hydroxy-5,10-dioxa-tetradecyl; C 1 -C 12 -alkylsulfanyl-C 1 -C 18 -alkyl, such as butylthiomethyl, 2-dodecylthioethyl, C 5 -C 12 -cycloalkyl-C 1 -C 18 -alkyl, such as cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3 cyclohexylpropyl, Phenyl-C 1 -C 6 -alkyl, where the phenyl moiety of phenyl-C 1 -C 6 -alkyl is unsubstituted or monosubstituted, disubstituted, trisubstituted or trisubstituted and the substituents independently of one another are C 1 -C 6 -alkyl, halogen, or C 6 -alkoxy and nitro are selected, such as benzyl (phenylmethyl), 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4- Dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, phenyl-C (CH ₃ ) 2-, 2,6-dimethylphenylmethyl, diphenyl-Ci-Cis-alkyl, such as diphenylmethyl (benzhydryl); Triphenyl-C 1 -C 18 -alkyl, such as triphenylmethyl;

Phenoxy-C 1 -C 6 -alkyl such as 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl;

Phenylthio-C 1 -C 18 -alkyl, such as 2-phenylthioethyl;

When R ¹ to R ^{9 are} C 2 -C alkenyl, R ¹ to R ^{9 are} preferably C 2 -C ⁶ -alkenyl, such as vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2- Butenyl or C2-Ci8 alkenyl which is partially or completely substituted by fluorine.

When R ¹ to R ^{9 are} Cβ-Cio-aryl, R ¹ to R ^{9 are} preferably phenyl or naphthyl, wherein phenyl or naphthyl is unsubstituted or mono-, di-, tri- or tetra-substituted, wherein the substituents independently of one another by halogen, C ₁ -C ₅ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylsulfanyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl,

Ci-Cβ-alkylcarbonyl, amino, Ci-Cε-alkylamino, di- (Ci-C6-dialkyl) amino and nitro are selected, such as phenyl, methylphenyl (ToIyI), dimethylphenyl (XyIyI), such as. For example, 2,6-dimethylphenyl, trimethylphenyl, such as. B. 2,4,6-trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, 2,6-dichlorophenyl , 4-bromophenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, 2,6-dimethoxyphenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl , Ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl, tert-butylthiophenyl, α-naphthyl, β-naphthyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, or partially fluorinated phenyl or perfluorinated phenyl.

When R ¹ to R ^{9 are} C 5 -C 12 -cycloalkyl, R ¹ to R ^{9 are} preferably unsubstituted cycloalkyl, such as cyclopentyl or cyclohexyl;

C 5 -C 12 -cycloalkyl which is monosubstituted or disubstituted, wherein the substituents are independently selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylsulfanyl or chlorine, eg. Butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl;

C5-C12-cycloalkyl which is completely or completely fluorinated. When R ¹ to R ^{9 are} polycyclyl, R ¹ to R ^{9 are} preferably C 5 -C 12 -cycloalkyl, such as norbornyl or C 5 -C 12 -cyclo-alkenyl, such as norbornenyl.

When R ¹ to R ⁹ are C5-Ci2-cycloalkenyl, then R ¹ to R ^{9 are} preferably unsubstituted cycloalkenyl, such as cyclopent-2-en-1-yl, cyclopent-3-en-1-yl, cyclohex-2 -en-1-yl, cyclohex-1-en-1-yl, cyclohexa-2,5-dien-1-yl or partially or fully fluorinated cycloalkenyl.

When R ¹ to R ^{9 are} heterocycloalkyl having 5 or 6 ring atoms, R ¹ to R ^{9 are} preferably 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1, 3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl.

When R ¹ to R ^{9 are} heteroaryl, R ¹ to R ^{9 are} preferably furyl, thienyl, pyrryl, pyridyl, indolyl, benzoxazolyl, benzimidazolyl, benzthiazolyl. In the case of a substitution hetaryl carries 1, 2 or 3 substituents which are independently selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and halogen, for example dimethylpyridyl, methylquinolyl, dimethylmethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.

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

Hydrogen;

unbranched or branched, unsubstituted or monosubstituted to polysubstituted by hydroxyl, halogen, phenyl, cyano, Ci-Cβ-alkoxycarbonyl and / or sulfo-substituted Ci-Cis-alkyl, 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-phenyl-propyl, 2-cyanoethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n- Butoxycarbonylmethyl, tert-butoxycarbonylmethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, Undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and 3-sulfopropyl; Hydroxyethyloxyalkyl, radicals of oligo- and polyalkylene glycols such as polyethylene glycols and polypropylene glycols and their oligomers having 2 to 100 units and a hydrogen or a Ci-Cs-alkyl as an 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 are preferably hydrogen, methyl or ethyl and n 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-tetraoxatetradecyl;

C ₂ -C ₄ alkenyl, such as vinyl and allyl; and

N, N-di-C 1 -C 6 -alkylamino, such as N, N-dimethylamino and N, N-diethylamino.

Most preferably, the radicals R ¹ to R ⁹ are each independently hydrogen; Ci-Ciβ-alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl; phenyl; 2-hydroxyethyl; 2-cyanoethyl; 2- (alkoxycarbonyl) ethyl such as 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl or 2- (n-butoxycarbonyl) ethyl; N, N- (C 1 -C 4 -dialkyl) amino, such as N, N-dimethylamino or N, N-diethylamino; Chlorine and for residues of oligoalkylene glycol, such as CH ₃ O- (CH ₂ CH ₂ O) _n -CH ₂ CH ₂ - or CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _n -CH ₂ CH ₂ - with n being the same 0 to 3.

Very particularly preferred pyridinium ions (IVa) 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 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.

Particularly preferred pyridinium ions (IVa) are pyridinium, 2-methylpyridinium, 2-ethylpyridinium, 5-ethyl-2-methylpyridinium and 2-methyl-3-ethylpyridinium and 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, t- (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, 9- (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-ethyl-pyridinium and 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1 - (1-Dodecyl) -methyl-S-ethyl-pyridinium, 1- (1-tetradecyl) -methyl-S-ethyl-pyridinium and 1- (1-hexadecyl) -methyl-S-ethyl-pyridinium.

Particularly preferred pyridazinium ions (IVb) are those in which the radicals 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 stand.

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, and R ² and R ^{4 is} methyl and R ^{3 is} hydrogen.

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, or

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

Hydrogen stands, or

R ¹ to R ^{4 are} methyl or

R ¹ to R ^{4 are} hydrogen.

Particularly preferred imidazolium ions (IVe) 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 stand.

Particularly suitable imidazolium ions (IVe) are 1-methylimidazolium, 1-ethylimidazolium, 1- (1-propyl) -imidazolium, 1- (1-allyl) -imidazolium, 1- (1-butyl) -imidazolium, 1 - (1 - Octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 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) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium , 1- (1-hexadecyl) -3-methylimidazolium, 1- (1 -hexade cyl) -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-dimethyl-imidazolium,

1 - (1-octyl) -2,3-dimethylimidazolium, 1, 4-dimethylimidazolium,

1, 3,4-trimethylimidazolium, 1, 4-dimethyl-3-ethylimidazolium, 3-methylimidazolium,

3-ethylimidazolium, 3-n-propylimidazolium, 3-n-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, 1, 4,5-trimethyl-3-octylimidazolium,

1-prop-1 -en-3-yl-3-methylimidazolium and 1-prop-1 -en-3-yl-3-butylimidazolium.

Particularly preferred pyrazolium ions (IVf), (IVg) or (IVg ') are those in which

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

Particularly preferred pyrazolium ions (IVh) are those in which R ¹ to R ⁴ independently of one another are hydrogen or methyl.

Particularly preferred pyrazolium ions are called pyrazolium and 1, 4-dimethylpyrazolium Particular preference is given in the inventive method as

1-pyrazolinium ions (IVi) are those in which

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

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 hydrogen or methyl.

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.

Particularly preferred imidazolinium ions (IV I) are those in which

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

Particularly preferred imidazolinium ions (IVm) or (IVm ') 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.

Particularly preferred imidazolinium ions (IVn) or (IVn ') are 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.

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.

When 1, 2,4-Triazoliumionen (IVq), (IVq ') or (IVq ") are particularly preferably used those in which

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

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

Particularly preferred pyrrolidinium ions (IVs) are those in which R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ⁹ independently of one another are hydrogen or methyl.

Particularly preferred imidazolidinium ions (IVt) are those in which R ¹ and R ⁴ independently of one another represent hydrogen, methyl, ethyl or phenyl and R ² , R ³ and R ⁵ to R ^{8 are} independently hydrogen or methyl.

Particular preference is given to using as ammonium ions (IVu) those in which R ¹ to R ³ independently of one another are C ¹ -C 6 -alkyl, or R ¹ and R ² together represent 1, 5-pentylene or 3-oxa-1, 5 -pentylene and R ^{3 is} selected from Ci-Cis-alkyl, 2-hydroxyethyl or 2-cyanoethyl.

Examples of the tertiary amines of which the quaternary ammonium ions of the general formula (IVu) are derived by quaternization with the radical R mentioned 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-ethylhexyl ) -amine, diisopropylethylamine, di-isopropyl-n-propylamine, di-isopropyl-butylamine, diisopropylpentylamine, 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-butylpyrrodidine, N-tert-butylpyrrolidine, Nn-pentylpyrrolidine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-di-n-butylcyclohexylamine, Nn-propylpiperidine, N-iso-propylpiperidine,

Nn-butyl-piperidine, 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, di-iso-propylbutylamine, 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.

Particularly preferred guanidinium ions (IVv) are those in which

R ¹ to R ^{5 are} methyl. An especially preferred guanidinium ion (IVv) is N, N, N ', N', N ", N" -hexamethylguanidinium.

Particular preference is given to using as cholinium ions (IVw) those in which R ¹ and R ² independently of one another are methyl, ethyl, 1-butyl or 1-octyl, and

R ^{3 is} hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ , or

R ^{1 is} methyl, ethyl, 1-butyl or 1-octyl; R ^{2 is} -CH ₂ -CH ₂ -OR ⁴ -; and

R ³ and R ⁴ independently of one another represent hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ , or R ^{1 represents} -CH ₂ -CH ₂ -OR ⁴ group, R ^{2 represents} 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 stand.

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, 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.

Particularly preferred are the cations (IV.x.1) selected from cations of

1, 5-diazabicyclo [4.3.0] non-5-ene (DBN) and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU).

Particularly preferred phosphonium ions (IVy) are those in which R ¹ to R ³ independently of one another are C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl, or phenyl which is unsubstituted or 1, 2, 3, 4 or 5 substituents, which are selected independently of one another from C 1 -C 6 -alkyl, carboxylate, sulfonate, COOH and SO ₃ H.

Particularly preferred sulfonium ions (IVz) are those in which R ¹ and R ^2, independently of one another, are C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.

Among the heterocyclic cations mentioned above, the imidazolium ions, imidazolinium ions, pyridinium ions, pyrazolinium ions and pyrazolium ions are preferred. Trains t. Particularly preferred are the imidazolium ions and cations of DBU and DBN.

As anions, in principle, all polyatomic anions, d. H. Polyatomic anions (anions with two or more than two atoms), can be used.

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

the group of pseudohalides and halogen-containing compounds of the formulas: BF ₄ ^" , PF ₆ ^" , CF ₃ SO ₃ -, (CF ₃ SOs) ₂ N-, CF ₃ CO ₂ ^" , CCI ₃ CO ₂ -, CN ^" , SCN ^" , OCN-;

the group of sulfates, sulfites and sulfonates of the general formulas: SO ₄ ^{2 "} , HSO ₄ -, SO ₃ ² -, HSO ₃ -, FK) SO ₃ -, R ^c SO ₃ -;

the group of phosphates of the general formulas: PO ₄ ^{3 "} , HPO ₄ ^2" , H ₂ PO ₄ -, R ³ PO ₄ ^{2 "} , HR ^C PO ₄ -, R ^c R ^d PO ₄ -;

the group of phosphonates and phosphinates of the general formulas: R ^c HPO ₃ -, R ^c R ^d PO ₂ -, R ^c R ^d PO ₃ -;

the group of phosphites of the general formulas: PO ₃ ^{3 "} , HPO ₃ ^2" , H ₂ PO ₃ -, R ^C PO ₃ ^{2 "} , R ^C HPO ₃ -, R ^c R ^d PO ₃ -;

the group of phosphonites and phosphinites of the general formulas: R ^c R ^d PO ₂ -, R ^c HPO ₂ -, R ^c R ^d PO ^" , R ^C HPO ^" ;

the group of carboxylic acids of the general formula: R ^C COO-;

Anions of hydroxycarboxylic acids and sugar acids;

Saccharinates (salts of o-benzoic acid sulfimide);

the group of borates of the general formulas: BO ₃ ^{3 "} , HBO ₃ ^2" , H ₂ BO ₃ -, R ^c R ^d BO ₃ -, R ^c HBO ₃ -, R ^c BO ₃ ^{2 "} , B (OR ^c ) (OR ^d) (OR ^e) (OR ^{f) ',} B (HSO _{4) 4} -, B (R ^C SO _{4) 4} -;

the group of boronates of the general formulas: R ^C BO ₂ ² -, R ^c R ^d BO-;

the group of carbonates and carbonic esters of the general formulas: HCO ₃ -, CO ₃ ² -, R ^c CO ₃ -; the group of silicates and silicic acid esters of the general formulas: SiO ₄ ^{4 "} , HSiO ₄ ^3" , H ₂ SiO ₄ ² -, H ₃ SiO ₄ -, R ^c Si0 ₄ ³ -, R ^c R ^d Si0 ₄ ² -, R ^c R ^d R ^e Si0 ₄ -, HR ^c Si0 ₄ ² -, H ₂ R ⁰ SiO ₄ -, HR ^c R ^d Si0 ₄ -;

the group of alkyl or aryl silanolates of the general formulas: R ^c Si0 ₃ ³ -, R ^c R ^d Si0 ₂ ² -, R ^c R ^d R ^e Si0 ^" , R ^c R ^d R ^e Si0 ₃ -, R ^c R ^d R ^e Si0 ₂ -, R ^c R ^d Si0 ₃ ² -;

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

NC

NC

the group of methides of the general formula:

SO ₂ -R ⁰

R ^e -O ₂ S 1 SO ₂ -R ^d

the group of alkoxides and aryloxides of the general formula RO-;

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

HS-, [Sv] ² -, [HSv] -, [R ^C S] -, where v is a whole positive number from 2 to 10.

The radicals R ^c , R ^d , R ^e and R ^f are preferably each independently

- hydrogen; Alkyl, preferably Ci-C3o-alkyl, particularly preferably Ci-Cis-alkyl, which is unsubstituted, or as defined above, is substituted, and / or, as defined above, may be interrupted by at least one heteroatom or heteroatom-containing group;

Aryl, preferably Cβ-C-u-Arvl, particularly preferably Cβ-Cio-aryl, which is unsubstituted, or as defined above, is substituted;

Cycloalkyl, preferably C5-C12 cycloalkyl which is unsubstituted or substituted as defined above;

Heterocycloalkyl, preferably heterocycloalkyl having 5 or 6 ring atoms, wherein the ring in addition to carbon ring atoms 1, 2 or 3 heteroatoms or heteroatom-containing groups which is unsubstituted, or as defined above, is substituted;

Heteroaryl, preferably heteroaryl having 5 to 10 ring atoms, wherein the ring in addition to carbon ring atoms 1, 2 or 3 heteroatom or heteroatom-containing groups which are selected from oxygen, nitrogen, sulfur and NR ^a , which is unsubstituted, or as defined above, is substituted ;

wherein in anions which have a plurality of radicals R ^c to R ^f , in each case two of these radicals together with the part of the anion to which they are attached represent at least one saturated, unsaturated or aromatic ring or a ring system having 1 to 12 carbon atoms may be wherein the ring or the ring system may have 1 to 5 non-adjacent heteroatoms or heteroatom-containing groups, which are preferably selected from oxygen, nitrogen, sulfur and NR ^a , and wherein the ring or the ring system is unsubstituted or may be substituted.

With regard to suitable and preferred C 1 -C 30 -alkyls, in particular C 1 -C 6 -alkyls, C 6 -C 14 -aryls, in particular C 6 -C 10 -cyclo, C 5 -C 12 -cycloalkyls, heterocycloalkyls having 5 or 6 ring atoms and heteroaryls having 5 or 6 Ring atoms is referred to the statements made at the outset. Regarding suitable and preferred substituents at d-Cso-alkyl, especially Ci-C ₈ alkyl, C ₆ -C ₂ aryl, C ₅ -C ₂ cycloalkyl, heterocycloalkyl with 5 or 6 ring atoms and heteroaryl with 5 or 6 ring atoms also referred to the statements made at the outset to substituents.

If at least one of the radicals R ^c to R ^{f is} optionally substituted C 1 -C 6 -alkyl, then it is preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hexadecyl, 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-methoxycarbonylethyl, 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-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-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.

If at least one of the radicals R ^c to R ^{f is} interrupted by one or more non-adjacent heteroatoms or heteroatom-containing interrupted Ci-cis-alkyl, it is preferably 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxa octyl, 11-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 1-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12- trioxa-pentadecyl,

9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxa-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-oxa-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-oxo nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

If two radicals R ^c to R ^{f 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.

The number of non-adjacent heteroatoms or heteroatom-containing groups of the radicals R ^c to R ^f is basically not critical and is usually limited only by the size of the respective residue or 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 are generally present between two heteroatoms.

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

Preferred functional groups of the radicals R ^c to R ^{f are} carboxy, carboxamide, hydroxy, di- (C 1 -C ₄ -alkyl) amino, C 1 -C ₄ -alkyloxycarbonyl, cyano or C 1 -C ₄ -alkoxy. Alkyl of different radicals R ^c to R ^f may also be mono- or polysubstituted by Ci-C ₄ -alkyl, preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

If at least one of the radicals R ^c to R ^{f is} optionally substituted C 6 -C 12 aryl, then it is preferably phenyl, methylphenyl (ToIyI), XyIyI, α-naphthyl, β-naphthyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, 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.

When at least one of R ^c to R ^{f is} optionally substituted

C 5 -C 12 -cycloalkyl, it preferably stands for 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.

If at least one of the radicals R ^c to R ^{f is} an optionally substituted five- or six-membered heterocycle, it preferably represents furyl, thienyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, Dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxifuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.

When in anions which have a plurality of radicals R ^c to R ^f , in each case two of these radicals together with the part of the anion to which they are attached represent at least one saturated, unsaturated or aromatic ring or a ring system having 1 to 12 carbon atoms can, wherein the ring or the ring system 1 to 5 non-adjacent heteroatoms or heteroatom-containing groups, which are preferably selected from oxygen, nitrogen, sulfur and NR ^a , the ring or the ring system is unsubstituted or carries 1, 2, 3, 4, 5 or more than 5 substituents. The substituents are preferably selected independently of one another are alkyl, alkoxy, alkylsulfanyl, cycloalkyl, cycloalkoxy, polycyclyl, heterocycloalkyl, aryl, aryloxy, arylthio and heteroaryl.

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

Preferred anions are formate, acetate, propionate, butyrate, lactate, saccharinate, carbonate, bicarbonate, sulfate, sulfite, C 1 -C 4 -alkyl sulfates, methanesulfonate, tosylate, trifluoroacetate, C 1 -C 4 -dialkyl phosphates and hydrogen sulfate.

Particularly preferred anions are HCOO-, CH ₃ COO-, CH ₃ CH ₂ COO-, dimethyl phosphate, diethyl phosphate, carbonate, bicarbonate, sulfate, sulfite, tosylate, CH ₃ SO ₃ - or CH ₃ OSO ₃ -.

Cations and anions are present in the ionic liquid. Within the ionic liquid, a proton or an alkyl radical is transferred from the cation to the anion. This creates two neutral molecules. Thus, there is an equilibrium in which there are anions, cations and the two neutral molecules formed therefrom.

The treatment medium used to modify the cellulosic material may comprise, in addition to at least one ionic liquid, at least one further solvent which is not an ionic liquid. The content of the treatment agent to further solvent is preferably in a range of 5 to 95 wt .-%, particularly preferably 10 to 80 wt .-%, in particular 15 to 60 wt .-%, based on the total weight of the treatment medium used.

If the liquid treatment medium comprises at least one further solvent, this is preferably at least partially miscible with the ionic liquid. Particularly preferably, the ionic liquid and the further solvent are completely miscible.

In a special embodiment of the process according to the invention, a liquid treatment medium is used which comprises at least one further solvent in which the solubility of the cellulosic material is lower under normal conditions (23 ^° C., 1 atm.) Than in the ionic liquid. Thus it can be prevented that an undesirably large amount of the cellulosic material is converted to a solubilized state.

Another solvent used is preferably a solvent or solvent mixture (precipitant) which is selected from water, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, diols and polyols, such as Ethanediol, propanediol and glycol, amino alcohols such as ethanolamine, diethanolamine and triethanolamine, aromatic solvents, eg. Benzene, toluene, ethylbenzene or xylenes, halogenated solvents, e.g. For example, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or chlorobenzene, aliphatic solvent, eg. Pentane, hexane, heptane, octane, ligroin, petroleum ether, cyclohexane and decalin, ethers, e.g. For example, tetrahydrofuran, diethyl ether, methyl tert-butyl ether and diethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, esters, eg. Ethyl acetate, and mixtures thereof. Preferably, the further solvent is selected from water, water-miscible organic solvents and mixtures thereof. Preferred water-miscible organic solvents are the abovementioned alcohols, in particular methanol and / or ethanol. In a first preferred embodiment, a water-containing medium is used as further solvent. Suitable hydrous media are water and mixtures of water and at least one water-miscible precipitant thereof. Especially preferred is water. In a second preferred embodiment, an organic solvent is used as a further solvent. Preference is given to the abovementioned alcohols, in particular methanol and / or ethanol.

The cellulose material used in the modification process according to the invention preferably has a cellulose content of at least 35% by weight, more preferably of at least 50% by weight. It goes without saying that the cellulosic material used according to the invention contains cellulose which can still undergo a structural change under treatment with at least one ionic liquid. Preferably, therefore, it is a non-pretreated with at least one ionic liquid cellulose.

The cellulosic material is preferably selected from cellulose, cellulosic natural materials, wood pulps, pulps, paper and paper-like products, cellulosic textiles and textile components, of which various cellulosic materials and combinations thereof.

As cellulose, in principle, any known form of cellulose can be used, for. B. from the cellulose materials mentioned below cellulose, regenerated cellulose, bacterial cellulose, etc. Suitable cellulosic natural substances are, for. As lignocellulosic materials, such as wood, including cellulose-containing natural fiber materials. Preference is given to cellulose-rich natural fiber materials, such as flax, Hemp, sisal, jute, straw, coconut fiber, switchgrass (panic virgatum) and other natural fibers. Under wood pulp fiber materials are wholly or predominantly made by mechanical means of wood, as they are known for. B. as a paper pulp (pulp) can be used. This includes z. B. wood pulp, brown wood pulp, refiner pulp and wood pulp with chemical pretreatment, such as chemical pulp and chemical refiner pulp. Pulp is understood to mean a fine-fiber mass with a high proportion of cellulose which results from the pulping of wood or other fiber materials. Pulp can z. For the inventive method, the pulps obtained by various pulping process, such as sulfite pulp, sulfate pulp, soda, nitric, etc., pulp of various provenances, such as Softwood pulp, hardwood pulp, straw pulp, etc. Also suitable are pulps characterized by different degrees of refinement, such as unbleached, bleached or bleached pulps. Specific pulp information may, for. B. evidence of the provenance and the digestion process in itself, such. B. in the statement spruce sulphite pulp. For the production of pulp, plant cellulosic materials are generally used and subjected to a digestion process for reducing non-cellulosic constituents, such as lignin, hemicellulose, polyoses, resins, etc. Paper and paper-like products, such as cardboard and board, are also suitable for use in the process according to the invention. The term paper is broadly understood and generally refers to a two-dimensional, essentially cellulosic fibers predominantly of vegetable origin material, which is formed by dewatering a pulp slurry and subsequent compaction and drying of the resulting fiber felt. Paper generally has a basis weight of up to 225 g / m ² . In contrast, the basis weight of paperboard is more than 225 g / m ² . Cardboard refers to a sheet material consisting of paper stock, which lies in its properties between paper and cardboard. Also, the weight per unit area of cardboard reaches into the area of the papers as well as into the cardboard. Cardboard is stiffer than paper and is generally made from higher quality materials than cardboard. Textiles and textile components are also suitable for use in the process according to the invention. The term textiles encompasses fibers for textile use, textiles (ie semi-finished and finished products made of fibers such as yarn or fabric) and finished textile goods (such as textile clothing, etc.). Textiles are generally made of fibers and are much more extended in two dimensions than in a third. Textile surfaces are generally referred to as fabrics and can be z. B. by weaving, knitting, knitting, fulling and solidifying to nonwoven fabric. For use in the method according to the invention are further suitable from the aforementioned cellulosic materials different cellulosic materials and existing materials. In a preferred embodiment, the cellulosic material is selected from wood, pulps, pulps, paper, paperboard, cardboard, and combinations thereof.

In a specific embodiment, the cellulosic material is paper or a paper-like product or cellulosic material which serves as a starting material for the production of paper and paper-like products.

Preferably, the process according to the invention particularly preferably at most 150 ⁰ C and in particular at most 120 ⁰ C. comprises treating the CeIIuIo- sematerials with at least one ionic liquid, as defined above, at a temperature not exceeding 200 ⁰ C, the treatment is preferably carried out at a temperature of at least 20 ^° C., more preferably at least 25 ^° C. A preferred temperature range is 25 to 120 ^° C .; a particularly preferred temperature range is 60 to 100 ^° C. The heating can be indirect or direct, preferably indirect. For direct heating, a hot, compatible with the ionic liquid used heat transfer fluid can be used. The indirect heating can be done with customary devices such. B. by heat exchangers, heat baths or microwave irradiation.

The pressure in the treatment of the cellulosic material with at least one ionic liquid is generally in a range of 0.1 bar to 100 bar, preferably 1 bar to 10 bar. In a special version, working at ambient pressure.

The duration of treatment of the cellulosic material with the ionic liquid is generally 0.5 minutes to 24 hours, preferably 1 to 300 minutes, especially 10 to 100 minutes. By choosing an appropriate, not too long duration of the treatment, it can be prevented that an undesirably large amount of the cellulosic material is converted into a solubilized state.

If only a small amount of ionic liquid is used to treat the cellulose material according to the process of the invention and / or if the modified cellulose material serves an application in which a residual amount of ionic liquid is not critical, separation of the liquid treatment medium after modification may be used partially or completely waived. In a preferred embodiment, however, the liquid treatment medium is at least partially separated from it after the modification of the cellulosic material.

The separation into a fraction containing the modified cellulose material and a liquid fraction containing the treatment agent takes place, for. B. by filtration. For acceleration, the filtration can be carried out under cellulosic side increased or expired sided reduced pressure. Likewise, the separation can be carried out by centrifugation. Usual centrifugation are z. See, for example, G. Hultsch, H. Wilkesmann, "Filtering Centrifuges," DB Purchas, Solid-Liquid Separation, Upland Press, Croydon 1977, pp. 493-559; and H. Trawinski in "The Equivalent Clarifying Surface of Centrifuges, Chem., Ztg., 83 (1959), 606-612." Various designs, such as tube and basket centrifuges and, in particular, thrust and inverting filter centrifuges and disc separators can be used.

The modified cellulosic material is preferably subjected to an additional treatment for the removal of ionic liquid still present following the separation of the treatment medium. For this purpose, the cellulosic material may for example be subjected to a wash with a liquid washing medium. Suitable washing media are those in which the ionic liquid dissolves well and cellulose or only in small amounts. Preferred washing media are the additional solvents described above. The washing medium is particularly preferably selected from water and mixtures of water and at least one water-miscible solvent thereof. Water is particularly preferably used as the washing medium.

If a liquid treatment medium is used to modify the cellulosic material, which contains at least one other solvent in addition to at least one ionic liquid and / or if the cellulosic material is subjected to a treatment with a liquid washing medium to remove any remaining ionic liquid, a liquid composition is obtained contains ionic liquid and a different solvent. This liquid composition is preferably subjected to separation into a fraction containing essentially the ionic liquid (I L1) and a fraction substantially containing the solvent (F1). This separation is usually carried out by evaporation of the precipitant, for. B. by distillation. Suitable separation devices are the customary distillation columns and evaporators, such as. B. falling film evaporator, forced circulation evaporator, short path evaporator or thin film evaporator. Owing to the low volatility of the ionic liquids, it is generally possible to dispense with complicated devices, such as those used in the separation of mixtures with boiling points which are close to one another, such as complicated column internals, columns with a high number of theoretical plates, etc. When using water as the precipitant, it is generally not necessary to subject the fraction containing the ionic liquid to additional drying due to the above-described tolerance of the ionic liquids used according to the invention to water.

By separating the liquid fraction into a fraction containing essentially the ionic liquid (I L1) and essentially the solvent Fraction (F1) containing generally at least 80 wt .-%, particularly preferably at least 90 wt .-%, in particular at least 93 wt .-% of the ionic liquid used in the treatment of the cellulosic starting material can be recovered. The fraction essentially containing the ionic liquid (I L1) is preferably used again for modifying the cellulosic starting material.

The fraction essentially containing the solvent can be used again as an additional solvent of the treatment medium used for modifying the cellulose material or as a washing medium.

In a preferred embodiment of the method according to the invention, the cellulosic material is subjected to grinding before, during and / or after being brought into contact with the liquid treatment medium. In a specific embodiment, the grinding of the cellulosic material takes place in the presence of the liquid treatment medium.

The grinding can be done in a suitable device, for example using a refiner. A refiner is a device for mechanically working fibers between rotating grinders at a controlled distance. The usually disk-shaped grinding devices can, for. B. be equipped with knives or Basaltlavamahlkörpern. One differentiates z. B. between Einscheibenrefinern, with only one rotating disc, and Doppelscheibenrefinern in which both discs rotate.

The determination of the degree of grinding can be made after a rough distinction in the grinding states "long and red", "short and red", "long and greasy" and "short and greasy". The exact determination of the freeness can be carried out in a known manner with a Mahlgradprüfgerät Schopper-Riegler. After grinding, the difference in freeness of the cellulose material is preferably at least 1 ⁰ SR weight, more preferably at least 10 ⁰ SR.

It has been found that when using milled fibers, the strengths of the products obtained, such as nonwovens, paper, cardboard, paperboard, etc. achieved by the fiber-fiber bond can be improved. It has thus been found that the use of fibers with a suitable freeness can at least partly eliminate the use of a strength-improving binder in the production of the products.

Another object of the invention is a process for the production of paper or a paper-like product, in which one a) providing a cellulose-containing starting material and bringing it into contact with a liquid treatment medium comprising at least one ionic liquid, wherein the bulk of the cellulosic material is not converted into a solubilized state,

b) subjecting the cellulosic material to grinding in the presence of the treatment medium,

c) optionally at least partially separating the liquid treatment medium,

d) optionally treating the cellulosic material with a liquid washing medium to remove any remaining ionic liquid,

e) producing a slurry from the cellulosic material by adding water and optionally further components,

f) further processing the slurry into paper or a paper-like product.

Step a)

The cellulose starting material provided in step a) is a material suitable for the production of paper and paper-like products, as is known to those skilled in the art, for example. B. under the name pulp is known. In principle, the pulps are subdivided into two groups: primary pulps, ie raw materials that are used for the first time in production, and secondary pulps, ie recycled materials, which are reused in the production process after use. In the provision of primary fiber materials can be z. B. emanating from groundwood, brown wood pulp, refiner wood pulp, wood pulp with chemical pretreatment, etc. When pulping wood, wood pulp or other fiber materials pulp falls with high cellulose content. For the preparation of the cellulose starting material in step a) are the customary, known to the expert pulping process, such as soda, sulfite, sulfate and Organozellverfahren, etc. Sulphate pulp is compared to sulfite pulp long-fiber and tear-resistant, so it is mainly for the Production of high white writing and printing papers used. Sulfite pulp finds predominantly use in the production of soft tissue papers. To remove residual lignin and other impurities, the cellulosic material may be subjected to further work-up. Restlignin and other undesirable substances may, for. For example, when bleaching is removed, chemical whitening removes discoloration. The bleaching of the pulp with chlorine is hardly used because of the high load of the waste water with organic chlorine compounds. Pulps obtained from bleaching with chlorine dioxide are also known as EC F-Ze 11 substances (elementary chlorides). ne free). Other suitable bleaching agents are, for. As oxygen, ozone, peroxoacetic acid, hydrogen peroxide, etc. The resulting pulp is referred to as TCF (totally chlorine free). Paper made from ECF pulps is called low in chlorine (there are still chlorine compounds). TCF pulp generally has lower fiber strength than chlorine-bleached or ECF pulp. Mainly made of wood pulp paper is called woody or medium fine. Since lignin, resins, fats and tannins remain in the pulp, they are of lesser quality than wood-free papers. The bleached pulp is usually dewatered.

If waste paper is used to provide the cellulosic starting material, this is generally first subjected to a work-up. This usually includes a mechanical processing of the so-called rags by sorting and cleaning in the Haderndrescher. Subsequently, the rags are heated, generally with addition of base (such as CaO, Ca (OH) 2, Na 2 CO 3, K 2 CO 3). Dyes are destroyed, saponified fats and dirt is dissolved. During several hours of cooking, the fabric of the rags loosens and they can then easily pulp into pulp, sorted by grades, bale pressed waste paper with a lot of water crushed and mechanically dissolved. Another suitable device for processing waste paper is the so-called pulper, a chest with rotating propeller. In it, waste paper is crushed with a lot of water and mechanically dissolved. This protects the fibers of the waste paper. An operation that used to be done frequently with the pug mill. The contaminated, pumpable pulp enters the pulper in a cylinder and is defibrated by a rotor. Then the coarsely dissolved substance is forced through a sieve. Due to the centrifugal force coarse impurities are deposited. At the cylinder axis, the light dirt collects. Other foreign substances such as waxes and printing inks are dissolved in special equipment. This includes the chemical treatment for deinking (deinking) of waste paper.

Step b)

The type of grinding essentially determines the property of the paper. In principle, a distinction can be made between a quick grinding and a greasy grinding. Another distinction is made according to the length of the fibers.

During fine grinding (short or long), the fibers are only cut in different lengths and the fiber structure is retained.

Use of the paper:

For a short reddish grind: z. B. Extinguishing, filter and hygiene papers; For long, redcurrant grind: z. B. printing papers. In greasy grinding (short or long), the fibers are squeezed and crushed.

Use of the paper:

For a short greasy grinding: z. Transparent paper, glassine;

For long greasy grinding: z. B. Typewriter, drawing and printing papers.

Step c)

With regard to the at least partial separation of the liquid treatment medium, reference is made to the previous statements on the separation into a fraction containing the modified cellulose material and a liquid fraction containing the treatment agent. Specifically, the separation is carried out by filtration. The separated treatment medium is preferably used again in step a).

Step d)

With regard to the treatment of the cellulosic material with a liquid washing medium for the removal of ionic liquid still contained, reference is made to the previous comments on this step.

Steps e and f)

Suitable further components for the production of paper and paper-like products are sizing agents, fillers, dyes and auxiliaries. Cellulosic material and other components, collectively referred to as stock, are diluted with water and then fed to the manufacture of paper or a paper-like material (eg cardboard, board). The production of paper takes place on paper machines, which usually comprise the following components:

• Headbox

• wire section

• Wet press section • Drying section

• Roll up

• To cut

The headbox spreads the highly diluted stock evenly across the entire width of the wire section. The paper components are applied so that a homogeneous fiber composite is formed. Through the wire of the wire section, there is a strong dewatering, while the fibers deposit next to each other and each other on the screen and form a sheet. The sieve structure is incorporated into the nonwoven fabric. To make the structure the same on both sides of the paper, there are twin-wire machines that extract water both up and down. Some papers receive a watermark at the end of the wire section by the draftsman.

In the press section, the further dewatering of the wet fiber fleece takes place by the pressure of roller pairs. The pressing process causes a compression of the paper structure and the strength is increased.

Drying section and reeling: The paper web runs like a slalom through the steam-heated drying cylinders and the remaining water is evaporated from the paper in a way that protects the fibers. In a size press inside the drying machine, the paper can be additionally surface-glued. To optimize the sheet thickness, the paper is passed through a roller calender and then rolled up.

Surface finishing (optional): Finishing takes place in the coating machine, where coating color is applied in excess to the base paper. A doctor blade ensures the correct coating weight and an optimal distribution of the coating color.

Smoothing: In the calender, the calendering of the coated paper takes place. Under pressure and temperature, the paper web is compressed in the calender and the paper thickness is reduced. This creates the shine and the paper is additionally smoothed.

Cut: on suitable cutting machines z. Roll cutters and cross cutters (eg from Vits Maschinenbau, Langenfeld, Germany), the paper rolls are cut to the width desired by the customer or shredded with a format cutter to sheet format.

The invention also provides the cellulosic materials obtainable by the processes described above, especially paper or paper-like products.

The invention will be explained in more detail by means of the following non-limiting examples.

Examples

As ionic liquids were

1) 1-ethyl-3-methylimidazolium acetate (EMI-AC)

2) 1-ethyl-3-methylimidazolium diethyl phosphate (EMI-DEP) used.

Wood pulp (Schopper-Riegler value 83.5 SR) and spruce pulp (31, 5 SR) are used as cellulosic material. The pulp had a dry content of 30%, it was subjected to disintegration by ZM V / 4/61 at 70000 min-. ¹

For the impregnation experiments described below, the cellulosic material was subjected to grinding with a Jokro mill with six refineries according to DIN 54 360-04 with 15 min grinding time each with deionized water. Subsequently, laboratory sheets were produced according to DIN EN ISO 5269 / 2-00 and the SR value was measured.

Grinding in the presence of ionic liquid:

For the grinding experiments, a 50 wt .-% mixture of ionic liquid and water was used. The oven-dried cellulose material (otro, 16 h at 105 ⁰ C) was soaked in water for 16 h and then pressed with extinguishing board until a dry content of about 40% was reached. The cellulosic material was then added to the preheated, dried grinding can and poured with 25 g of a mixture of water and ionic liquid (50%) heated to the boiling point of the water. After milling for 15 min, it was made up to 2 l with deionized water and disintegrated for 2 min at 70,000 min ^-1 . Subsequently, handsheets were prepared and the SR value was measured.

Drinking with ionic liquid:

For the impregnation experiments, a 50 wt .-% mixture of ionic liquid and water was used. A laboratory sheet prepared by the standard milling described above without the presence of an ionic liquid was soaked with the treatment solution at room temperature for 1 minute. The sheet was allowed to dry, sucked off the excess liquid with blotter and then dried for 10 min in Rapid-Kothen-T rocker at 93 ⁰ C.

Washing after impregnation:

The sheets obtained by the soaking process described above were washed in the Rapid-Köthen sheet former. To this was added 2 l of water to the leaf, aspirated and the process then repeated once. Subsequently, the washed sheet was 10 min in Rapid-Kothen T Rockner at 93 ⁰ C under vacuum getrock- net.

Used test standards: Milling with the Jokro mill: DIN 54 360-04 (based on ionic waters to this standard)

SR value: ZM VI / l / 66

Laboratory sheet formation: DIN EN ISO 5269 / 2-00

Disintegrate: ZM V / 4/61

Used abbreviations:

MW = mean s = standard deviation

V = coefficient of variation

DIN = German Institute for Standardization e. V., Berlin

ZM = test specification of the association Zellcheming. Darmstadt

EN = European standard

ISO = International Organization for Standardization, Geneva

Air conditioning in normal climate 23 ⁰ C and 50% relative humidity (23/50 - 1 according to DIN EN 20 187-93)

Table 1: Wood pulp (83.5 SR)

"Examination of 1-2 handsheets

Table 2: Soaking without / with subsequent washing

Prüfung von nur je einem Laborblatt

Testing only one lab sheet at a time

Table 3: spruce sulphite pulp (31, 5 SR)

"Examination of 1-2 handsheets

Claims

claims A method of modifying the structure of a cellulosic material by contacting it with a liquid treatment medium comprising at least one ionic liquid, wherein the bulk of the cellulosic material is not converted to a solubilized state. 2. The method of claim 1, wherein at least one ionic liquid is used, which is selected from (A) Salts of General Formula (I) [A]; [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 polyatomic, one, bi-, tri- or tetravalent anion or mixtures of these anions; (B) mixed salts of the general formulas (II.a), (II.b) or (II.c) [A ¹ J ⁺ [A ² J ⁺ [Y] "- (I I. a), where n = 2, [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] "- (II b), where n = 3, [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] "- (I I. c), where n = 4, and wherein [A ¹ J ⁺ , [A ² ] ⁺ , [A ³ J ⁺ and [A ⁴ J ^{+ 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) to (III.j) [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [M ¹ ] ⁺ [Y] - (II La), where n = 4, [A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] - (MLb), where n = 4, [A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [M ³ ] ⁺ [Y] "- (111 c), where n = 4, [A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [Y] "- (III.d), where n = 3, [A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] "- (MLe), where n = 3, [A ¹ ] ⁺ [M ¹ ] ⁺ [Y] - (II Lf), where n = 2, [A ¹ ] ⁺ [A ² ] ⁺ [M ⁴ ] ²⁺ [Y] "- (II Lg), where n = 4, [A ¹ ] ⁺ [M ¹ ] ⁺ [M ⁴ ] ²⁺ [Y] "- (MLh), where n = 4, [A ¹ ] ⁺ [M ⁵ ] ³⁺ [Y]" - (MLi) where n = 4, [A ¹ ] ⁺ [M ⁴ ] ²⁺ [Y] "- (III.j), where n = 3, and wherein [A ¹ ] ⁺ , [A ² ] ⁺ and [A ³ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ , [Y] ⁿ "has the meaning mentioned under (A) and [IVP] ⁺ , [M ² J ⁺ , [M ³ ] ⁺ monovalent metal cations, [M ⁴ J ²⁺ divalent metal cations and [M ⁵ J ³⁺ trivalent metal cations. 3. The method according to any one of claims 1 or 2, wherein at least one ionic liquid is used which has at least one cation selected from compounds of the formulas (IV.a) to (IV.z),

(IV.d) (IV.e)

(IV.k) (IV.k ') (IV.I)

(IV.m) (IV.m ¹⁾ (IV s)

(IV.rϊ) (IV.o) (IV.o ¹ )

(IV.p) (IV.q) (IV.q ¹⁾

(IV.q ") (IV.r) (IV.r ')

(IV.r ") (IV.s) (IV.t)

(IV.u) (IV.v) (IV.w)

(IV.x.1) (IV.x.2)

(IV.y) (IV.z) and oligomers containing these structures, wherein R represents hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, polycyclyl, heterocycloalkyl, aryl or heteroaryl, Radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ attached to a ring carbon atom independently of one another represent hydrogen, a sulfo group, COOH, carboxylate, sulfonate, acyl , Alkoxycarbonyl, cyano, halogen, hydroxyl, SH, nitro, NE ¹ E ² , alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, polycyclyl, polycycloxy, heterocycloalkyl, aryl, aryloxy or Heteroaryl, where E ¹ and E ² independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ attached to a ring heteroatom are independently hydrogen, SO 3 H, NE ¹ E ² , alkyl, alkoxy , Alkenyl, cycloalkyl, cycloalkenyl, polycyclyl, heterocycloalkyl, aryl or heteroaryl, where E ¹ and E ² are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or two adjacent radicals R ¹ to R ⁹ together with the ring atoms to which they are attached, for at least one fused, saturated, unsaturated or aromatic ring or a ring system having 1 to 30 carbon atoms. wherein the ring or the ring system may have from 1 to 5 non-adjacent heteroatoms or heteroatom-containing groups and where the ring or the ring system may be unsubstituted or substituted, where two geminal radicals R ¹ to R ^{9 can} also together stand for = 0, = S or = NR ^b , where R ^{b is} hydrogen, alkyl, cycloalkyl, aryl or heteroaryl, where in the compounds of the formula (IV.x.1) R ¹ and R ³ or R ³ and R ^{5 may} also together be the bond moiety of a double bond between the ring atoms which carry these radicals, B in the compounds of the formulas (IV.x.1) and (IV.x.2) together with the CN group to which it is attached forms a 4- to 8-membered, saturated or unsaturated or aromatic cycle, which is optionally substituted and / or which may optionally have further heteroatoms or heteroatom-containing groups and / or which may comprise further fused saturated, unsaturated or aromatic carbocycles or heterocycles. 4. The method according to claim 3, wherein at least one ionic liquid is used which has at least one cation selected from imidazolium ions of the formulas (IV, e). 5. The method according to any one of the preceding claims, wherein at least one ionic liquid is used which has at least one anion which is selected from: the group of pseudohalides and halogenated compounds of Formulas: BF ₄ ^", PF ^_6", CF ₃ SO ₃ -, (CF ₃ SOs) ₂ N-, CF ₃ CO ₂ ^", CCl ₃ CO ₂ -, ^CN", SCN ^", OCN; the group of sulfates, sulfites and sulfonates of the general formulas: SO ₄ ^{2 "} , HSO ₄ -, SO ₃ ^2" , HSO ₃ -, R ^C OSO ₃ -, R ^c SO ₃ -; the group of phosphates of the general formulas: PO ₄ ^{3 "} , HPO ₄ ^2" , H ₂ PO ₄ -, R ³ PO ₄ ^{2 "} , HR ^C PO ₄ -, R ^c R ^d PO ₄ -; - the group of phosphonates and phosphinates of the general formulas: R ^c HPO ₃ -, R ^c R ^d PO ₂ -, R ^c R ^d PO ₃ -; the group of phosphites of the general formulas: PO ₃ ^{3 "} , HPO ₃ ^2" , H ₂ PO ₃ -, R ^c POs ² -, R ⁰ HPO ₃ -, R ^c R ^d PO ₃ -; the group of phosphonites and phosphinites of the general formulas: R ^c R ^d PO ₂ ^" , R ^C HPO ₂ -, R ^c R ^d PO ^" , R ^C HPO ^" ; the group of carboxylic acids of the general formula: R ^C COO-; Anions of hydroxycarboxylic acids and sugar acids; Saccharinates (salts of o-benzoic acid sulfimide); the group of borates of the general formulas: BO ₃ ^{3 "} , HBO ₃ ^2" , H ₂ BO ₃ -, R ^c R ^d BO ₃ -, R ^c HBO ₃ -, R ^c BO ₃ ^{2 "} , B (OR ^c) (OR ^d) (OR ^e) (OR ^f) -, B (HSO ₄ K, B (R ^C SO _{4) 4} -; the group of boronates of the general formulas: R ^C BO ₂ ² -, R ^c R ^d BO- the group of carbonates and carbonic esters of the general formulas: HCO ₃ -, CO ₃ ² -, R ^c 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 ^c Si0 ₄ ³ -, R ^c R ^d Si0 ₄ ² -, R ^c R ^d R ^e SiO ₄ -, HR ^c Si0 ₄ ² -, H ₂ R ^c Si0 ₄ -, HR ^c R ^d Si0 ₄ -; the group of the alkyl or aryl silanolates of the general formulas: R ^c Si0 ₃ ³ -, R ^c R ^d Si0 ₂ ² -, R ^c R ^d R ^e SiO ^" , R ^c R ^d R ^e SiO ₃ -, R ^c R ^d R ^e SiO ₂ -, R ^c R ^d Si0 ₃ ² - the group of carboximides, bis (sulfonyl) imides and sulfonylimides of the general formula: NC N ^C

the group of methides of the general formula: SO ₂ -R ⁰ R ^e -O, S 1 SO ₂ -R ^d the group of alkoxides and aryloxides of the general formula RO ^" ; the group of hydrogen sulfides, polysulfides, hydrogen polysulfides and thiolates of the general formulas: HS-, [Sv] ^{2 "} , [HSv] ^" , [R ^C S] -, where v is a whole positive number from 2 to 10, wherein the radicals R ^c , R ^d , R ^e and R ^{f are} independently selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, wherein in anions which have a plurality of radicals R ^c to R ^f , in each case two of these radicals together with the part of the anion to which they are bonded, for at least one, saturated, unsaturated or aromatic ring or a ring system having 1 to 12 carbon atoms may be, wherein the ring or the ring system may have 1 to 5 non-adjacent heteroatoms or heteroatom-containing groups, which are preferably selected from oxygen, nitrogen, sulfur and NR ^a , and wherein the ring or the ring system is unsubstituted or may be substituted. 6. The method according to any one of the preceding claims, wherein one uses a treatment medium, which additionally comprises at least one other of the ionic liquid different solvent. 7. The method of claim 6, wherein at least one further solvent is used, which is at least partially miscible with the ionic liquid. 8. The method according to any one of claims 6 or 7, wherein at least one further solvent is used in which the solubility of the cellulosic material under normal conditions is lower than in the ionic liquid. 9. The method according to any one of claims 6 to 8, wherein the further solvent is selected from water, water-miscible organic solvents and mixtures thereof. 10. The method according to any one of the preceding claims, wherein the cellulosic material used for the modification has a cellulose content of at least 35 wt .-%, preferably of at least 50 wt .-%, having. 1 1. The method according to any one of the preceding claims, wherein the cellulosic material is selected from cellulose, cellulosic natural materials, wood pulp, cellulose, paper and paper-like products, cellulosic textiles and textile components, including various cellulosic materials and existing materials and combinations thereof. The method of claim 11, wherein the cellulosic material is selected from wood, pulps, pulps, paper, paperboard, cardboard, and combinations thereof. 13. The method according to any one of the preceding claims, wherein the modification of the cellulosic material at a temperature of 25 to 120 ⁰ C, preferably 60 to 100 ⁰ C, takes place. 14. The method according to any one of the preceding claims, wherein the liquid treatment medium after the modification of the cellulosic material is at least partially separated therefrom. 15. The method of claim 14, wherein the separated liquid treatment medium is used again to modify a cellulosic material. 16. The method according to any one of the preceding claims, wherein subjecting the cellulosic material before, during and / or after contacting with the liquid treatment medium of a grinding. 17. A method of modifying the structure of paper or a paper-like product by contacting it with a liquid treatment medium comprising at least one ionic liquid, wherein the bulk of the cellulosic material is not converted to a solubilized state. 18. A process for the production of paper or a paper-like product, in which one a) providing a cellulosic starting material and contacting it with a liquid treatment medium comprising at least one ionic liquid, wherein the bulk of the cellulosic material is not converted to a solubilized state, b) subjecting the cellulosic material to grinding in the presence of the treatment medium, c) optionally at least partially separating off the liquid treatment medium, d) optionally treating the cellulosic material with a liquid washing medium to remove any remaining ionic liquid, e) producing a slurry from the cellulosic material by adding water and optionally further components, f) further processing the slurry into paper or a paper-like product. 19. Cellulosic material obtainable by a process according to any one of claims 1 to 16. 20. Paper or paper-like product obtainable by a process according to claim 17 or 18.