DE102006030696A1 - Acylating poly- or oligo- saccharide comprises dissolving the saccharide in an ionic liquid, treating the mixture with an acid under the supplement of water, and treating the obtained saccharide with an acylating agent - Google Patents

Abstract

Acylating poly- or oligo- saccharide comprises dissolving poly- or oligo- saccharide in at least an ionic liquid (A), treating the mixture with at least an acid under the supplement of water at high temperature, and treating the obtained poly- or oligo- saccharide having polymerization degree lower than the used poly- or oligo- saccharides, with an acylating agent.

Description

The The present invention describes a process for the acylation of Cellulose with a specific average degree of polymerization (DP), by being in an ionic liquid Cellulose in a first step targeted degradation and in a second step of an acylation.

cellulose is the most important renewable resource and represents an important Starting material for example the textile, paper and nonwovens industries. It also serves as raw material for Derivatives and modifications of cellulose, which include cellulose ethers, such as. Methylcellulose and carboxymethylcellulose, cellulose esters based on organic acids, such as. Cellulose acetate, cellulose butyrate, and cellulose esters based on inorganic acids, such as. Cellulose nitrate, and others count. These derivatives and modifications find diverse Application, for example in the textile, food, construction and Coatings industry. Of particular interest here is cellulose acetate.

at The industrial production of cellulose acetate becomes cotton linters or recycled wood pulp with acetic anhydride in the presence of sulfuric acid or perchloric acid implemented as a catalyst. This procedure occurs both a decrease of the DP as well as an acylation of the hydroxy functions the anhydroglucan units of cellulose. The decrease of the chain length of the Cellulose base body is due to a hydrolytic cleavage of the glycosidic bonds, as a consequence of the strongly acidic reaction conditions, attributed. Farther the cellulose acetate thus obtained has a degree of substitution (DS) of 3 (= cellulose triacetate). For however, spinning requires a DS of about 2.5. Therefore Cellulose triacetate is subjected to partial deacylation. The disadvantage here is that in this process initially a heterogeneous mixture is present, which in the course of the reaction in a more or less homogeneous mixture passes. The handling of such Mixtures makes very high technical demands. It is the same of disadvantage that primary a cellulose acetate having a DS of 3 is obtained. Farther depends on that DP of the obtained cellulose acetate is strongly dependent on the quality of the used Cellulose and the reaction conditions.

Consequently there is a need, a simple method of targeted representation of acylated celluloses with a targeted DP and a defined To provide DS.

It has now become a method for the preparation of acylated celluloses found with a targeted DP and a defined DS by Dissolving cellulose in an ionic liquid, and the solution thus obtained in a first step (step A) with an acid (optionally with the addition of Water) or at elevated Temperature (if necessary in the presence of water) and treated in one second step (step B) the cellulose thus obtained, whose DP is lower than that of the cellulose used in step A, reacted with an acylating agent.

• (A) Salze der allgemeinen Formel (I) [A] + / n[Y]^n– (I), in der n für 1, 2, 3 oder 4 steht, [A]⁺ für ein quartäres Ammonium-Kation, ein Oxonium-Kation, ein Sulfonium-Kation oder ein Phosphonium-Kation und [Y]^n– für ein ein-, zwei-, drei- oder vierwertiges Anion steht;
• (B) gemischte Salze der allgemeinen Formeln (II) [A¹]⁺[A²]⁺[Y]^n– (IIa), wobei n = 2; [A¹]⁺[A²]⁺[A³]⁺[Y]^n– (IIb), wobei n = 3; oder [A¹]⁺[A²]⁺[A³]⁺[A⁴]⁺[Y]^n– (IIc), wobei n = 4 und wobei [A¹]⁺, [A²]⁺, [A³]⁺ und [A⁴]⁺ unabhängig voneinander aus den für [A]⁺ genannten Gruppen ausgewählt sind und [Y]^n– die unter (A) genannte Bedeutung besitzt.

Ionic liquids in the sense of the present invention are preferred

• (A) Salts of the general formula (I) [A] + / n [Y] ^n- (I) in which 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- for a bi-, tri- or tetravalent anion is;
• (B) mixed salts of the general formulas (II) [A ¹ ] ⁺ [A ² ] ⁺ [Y] ^n- (IIa) where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ^n- (IIb) where n = 3; or [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ^{n -} (IIc) where n = 4 and wherein [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ and [Y] ^{n -} the has meaning given by (A).

Preferably own the ionic liquids a melting point of less than 180 ° C. Particularly preferred is the melting point in a range of -50 ° C to 150 ° C, particularly preferably in the range from -20 ° C to 120 ° C and extraordinary preferably below 100 ° C.

at the inventive ionic liquids these are organic compounds, i. that at least a cation or an anion of the ionic liquid is an organic one Contains rest.

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

In the case, that the nitrogen atom of the carrier is the positive charge in the cation of the ionic liquid can, at the Synthesis of ionic liquids first quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle produces a cation become. The quaternization can be achieved by alkylation of the nitrogen atom respectively. Depending on the Alkylierungsreagens used salts with different Get anions. In cases, in which it is not possible is, the desired Anion already formed during quaternization, this can be done in one further synthesis step. Starting, for example, from an ammonium halide, the halide can be reacted with a Lewis acid become, whereby from halide and Lewis acid a complex anion formed becomes. Alternatively, the replacement of a halide ion against the wished Anion possible. This can be done by adding a metal salt with precipitation of the formed metal halide, about an ion exchanger or by displacement of the halide ion by a strong acid (With liberation of the hydrohalic acid) happen. Suitable methods are for example in Angew. Chem. 2000, 112, pp. 3926-3945 and the literature cited therein.

Suitable alkyl radicals with which the nitrogen atom in the amines or nitrogen heterocycles may be quaternized, for example, are C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₁₀ -alkyl, more preferably C ₁ -C ₆ -alkyl, and very particularly preferably Methyl. The alkyl group may be unsubstituted or have one or more identical or different substituents.

Prefers are those compounds which contain at least one 5- to 6-membered heterocycle, in particular a five-membered one Heterocycle, containing at least one nitrogen atom as well optionally an oxygen or sulfur atom. Also those compounds which are at least one of them are particularly preferred five to contain six-membered heterocycle, the one, two or three Has nitrogen atoms and a sulfur or an oxygen atom, most preferably those having two nitrogen atoms. Farther preferred are aromatic heterocycles.

Especially preferred compounds are those having a molecular weight below 1000 g / mol, most preferably below 500 g / mol and in particular below 350 g / mol.

sowie Oligomere, die diese Strukturen enthalten.Furthermore, preference is given to those cations which are selected from the compounds of the formulas (IIIa) to (IIIw)

and oligomers containing these structures.

sowie Oligomere, die diese Strukturen enthalten.Further suitable cations are compounds of the general formula (IIIx) and (IIIy)

and oligomers containing these structures.

• • der Rest R für Wasserstoff, einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen; und
• • die Reste R¹ bis R⁹ unabhängig voneinander für Wasserstoff, eine Sulfo-Gruppe oder einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder ar aliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen, wobei die Reste R¹ bis R⁹, welche in den oben genannten Formeln (III) an ein Kohlenstoffatom (und nicht an ein Heteroatom) gebunden sind, zusätzlich auch für Halogen oder eine funktionelle Gruppe stehen können; oder zwei benachbarte Reste aus der Reihe R¹ bis R⁹ zusammen auch für einen zweibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen.

In the abovementioned formulas (IIIa) to (IIIy)

• • the radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms; and
• • the radicals R ¹ to R ^{9 are} independently hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups substituted radicals having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) are bonded to a carbon atom (and not to a heteroatom), additionally may also stand for halogen or a functional group; or two adjacent radicals from the series R ¹ to R ⁹ together also represent a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups with 1 to 30 carbon atoms.

Suitable hetero atoms in the definition of the radicals R and R ¹ to R ^{9 are in} principle all heteroatoms in question which are capable of formally a -CH ₂ -, a -CH =, a -C≡ or a = C = group to replace. When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. Particularly preferred groups which may be mentioned are -O-, -S-, -SO-, -SO ₂ -, -NR'-, -N =, -PR'-, -PR ' ₃ and -SiR' ₂ -, where the radicals R 'are the remainder of the carbon-containing radical. The radicals R ¹ to R ⁹ are, in the cases in which they are in the above formulas (III) to a carbon atom (and not to a heteroatom) attached, also be bound directly via the heteroatom.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. Suitable examples are -OH (hydroxy), = O (especially as carbonyl group), -NH ₂ (amino), -NHR ', -NR 2', = NH (imino), = NR ', -COOH (carboxy), - CONH ₂ (carboxamide), -SO ₃ H (sulfo) and -CN (cyano). Fractional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide) or -CONR'- (tertiary amide), are included, for example, di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ alkyloxycarbonyl or C ₁ -C ₄ alkyloxy. The R 'radicals are the remainder of the carbon-containing radical.

When Halogens are called fluorine, chlorine, bromine and iodine.

• • unverzweigtes oder verzweigtes, unsubstituiertes oder ein bis mehrfach mit Hydroxy, Halogen, Phenyl, Cyano, C₁-C₆-Alkoxycarbonyl und/oder SO₃H substituiertes C₁-C₁₈-Alkyl mit insgesamt 1 bis 20 Kohlenstoffatomen, wie beispiels weise Methyl, Ethyl, 1-Propyl, 2-Propyl, 1-Butyl, 2-Butyl, 2-Methyl-1-propyl, 2-Methyl-2-propyl, 1-Pentyl, 2-Pentyl, 3-Pentyl, 2-Methyl-1-butyl, 3-Methyl-1-butyl, 2-Methyl-2-butyl, 3-Methyl-2-butyl, 2,2-Dimethyl1-propyl, 1-Hexyl, 2-Hexyl, 3-Hexyl, 2-Methyl-1-pentyl, 3-Methyl-1-pentyl, 4-Methyl-1-pentyl, 2-Methyl-2-pentyl, 3-Methyl-2-pentyl, 4-Methyl-2-pentyl, 2-Methyl-3-pentyl, 3-Methyl-3-pentyl, 2,2-Dimethyl-1-butyl, 2,3-Dimethyl-1-butyl, 3,3-Dimethyl-1-butyl, 2-Ethyl-1-butyl, 2,3-Dimethyl-2-butyl, 3,3-Dimethyl-2-butyl, 1-Heptyl, 1-Octyl, 1-Nonyl, 1-Decyl, 1-Undecyl, 1-Dodecyl, 1-Tetradecyl, 1-Hexadecyl, 1-Octadecyl, 2-Hydroxyethyl, Benzyl, 3-Phenylpropyl, 2-Cyanoethyl, 2-(Methoxycarbonyl)-ethyl, 2-(Ethoxycarbonyl)-ethyl, 2-(n-Butoxy-carbonyl)-ethyl, Trifluormethyl, Difluormethyl, Fluormethyl, Pentafluorethyl, Heptafluorpropyl, Heptafluorisopropyl, Nonafluorbutyl, Nonafluorisobutyl, Undecylfluorpentyl, Undecylfluorisopentyl, 6-Hydroxyhexyl und Propylsulfonsäure;
• • Glykole, Butylenglykole und deren Oligomere mit 1 bis 100 Einheiten und einem Wasserstoff oder einem C₁-C₈-Alkyl als Endgruppe, wie beispielsweise R^AO-(CHR^B-CH₂-O)_m-CHR^B-CH₂- oder R^AO-(CH₂CH₂CH₂CH₂O)_m-CH₂CH₂CH₂CH₂- mit R^A und R^B bevorzugt Wasserstoff, Methyl oder Ethyl und m bevorzugt 0 bis 3, insbesondere 3-Oxabutyl, 3-Oxapentyl, 3,6-Dioxaheptyl, 3,6-Dioxaoctyl, 3,6,9-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9,12-Tetraoxatridecyl und 3,6,9,12-Tetraoxatetradecyl;
• • Vinyl;
• • 1-Propen-1-yl, 1-Propen-2-yl und 1-Propen-3-yl; und
• • N, N-Di-C₁-C₆-alkyl-amino, wie beispielsweise N,N-Dimethylamino und N,N-Diethylamino.

The radical R preferably stands for

• • straight-chain or branched, unsubstituted or monosubstituted to polysubstituted by hydroxyl, halogen, phenyl, cyano, C ₁ -C ₆ alkoxycarbonyl and / or SO ₃ H substituted C ₁ -C ₁₈ alkyl having a total of 1 to 20 carbon atoms, such as example Methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl Methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2 Methyl 3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1 butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl l, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;
• Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C ₁ -C ₈ -alkyl as end group, such as R ^A O- (CHR ^B -CH ₂ -O) _m -CHR ^B -CH ₂ - or R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^B preferably hydrogen, methyl or ethyl and m preferably 0 to 3, in particular 3-oxabutyl , 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12 -Tetraoxatetradecyl;
• • vinyl;
• 1-propen-1-yl, 1-propen-2-yl and 1-propen-3-yl; and
• N, N-di-C ₁ -C ₆ -alkyl-amino, such as N, N-dimethylamino and N, N-diethylamino.

Particularly preferably, the radical R is unbranched and unsubstituted C ₁ -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, 1-propen-3-yl, in particular methyl, ethyl, 1-butyl and 1-octyl and CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - with m equal to 0 to 3.

• • Wasserstoff;
• • Halogen;
• • eine funktionelle Gruppe;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes und/oder durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₁-C₁₈-Alkyl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes und/oder durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₂-C₁₈-Alkenyl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₆-C₁₂-Aryl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₅-C₁₂-Cycloalkyl;
• • gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₅-C₁₂-Cycloalkenyl; oder
• • einen gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituierten fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus bedeuten; oder zwei benachbarte Reste zusammen für
• • einen ungesättigten, gesättigten oder aromatischen, gegebenenfalls durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituierten und gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenen Ring.

The radicals R ¹ to R ⁹ are preferably each independently

• • hydrogen;
• • halogen;
• • a functional group;
• Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₁ -C _18- alkyl;
• Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C ₁₈ alkenyl;
• Optionally C ₆ -C ₁₂ -aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles;
• Optionally C ₅ -C ₁₂ -cycloalkyl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles;
• Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₅ -C ₁₂ cycloalkenyl; or
• • an optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five to six-membered, oxygen, nitrogen and / or sulfur atoms having heterocycle; or two adjacent radicals together for
• • an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally ring interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₁ -C ₁₈ alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3 Methyl 1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1 -pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl , 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3 Dimethyl 2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, 1-nonyl, 1-decyl , 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylme methyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, α, α-dimethylbenzyl, p-tolylmethyl, 1- (p-butylphenyl ) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl ) -ethyl, methoxy, ethoxy, formyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1, 3-dioxolan-2-yl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2- Methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2- Phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, acetyl, C _m F _{2 (m-a) + (1-b)} H _{2a + b} with m being 1 to 30, 0 ≤ a ≤ m and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C _{( m - 2)} F _{2 (m - 2) + 1} , C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ ), chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl-2 -chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n- Butoxycarbonyl) -ethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxo-octyl, 11-hydroxy-3,6,9-trioxa-undecyl , 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5 , 10-dioxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-metho xy-3,6-dioxo-octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy 4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6- dioxo-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12- trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxatetradecyl.

In optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C _18- alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F _{2 (m - a) - (1 - b)} H _{2a - b} with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₆ -C ₁₂ aryl is preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4- Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, t-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6 Dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl , 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _(5-a) H _a with 0 ≤ a ≤ 5.

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₅ -C ₁₂ cycloalkyl is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F _{2 (m - a) - (1 - b)} H _{2a - b} with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1 and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

C ₅ -C ₁₂ -cycloalkenyl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2.5- Cyclohexadienyl or C _n F _{2 (m - a) - 3 (1 - b)} H _{2a - 3b} with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

at optionally substituted by functional groups, aryl, alkyl, aryloxy, Alkyloxy, halogen, heteroatoms and / or heterocycles substituted five to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, Pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, Benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, Dimethoxypyridyl or difluoropyridyl.

Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more several substituted or unsubstituted imino groups interrupted ring, it is preferably 1,3-propylene, 1,4-butylene, 1,5-pentylene, 2-oxa-1,3-propylene, 1-oxa-1,3- propylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propenylene, 3-oxa-1,5-pentylene, 1-aza-1,3-propenylene, 1-C ₁ -C ₄ - Alkyl 1-aza-1,3-propenylene, 1,4-buta-1,3-dienylene, 1-aza-1,4-buta-1,3-dienylene or 2-aza-1,4-butane 1.3 dienylene.

Contain the abovementioned radicals oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number is the oxygen and / or Sulfur atoms and / or imino groups not limited. As a rule, it is not more than 5 in the remainder, preferably not more than 4 and more especially preferably not more than 3.

Contain the above-mentioned radicals heteroatoms, so are between two heteroatoms usually at least one carbon atom, preferably at least two carbon atoms.

• • Wasserstoff;
• • unverzweigtes oder verzweigtes, unsubstituiertes oder ein bis mehrfach mit Hydroxy, Halogen, Phenyl, Cyano, C₁-C₆-Alkoxycarbonyl und/oder SO₃H substituiertes C₁-C₁₈-Alkyl mit insgesamt 1 bis 20 Kohlenstoffatomen, wie beispielsweise Methyl, Ethyl, 1-Propyl, 2-Propyl, 1-Butyl, 2-Butyl, 2-Methyl-1-propyl, 2-Methyl-2-propyl, 1-Pentyl, 2-Pentyl, 3-Pentyl, 2-Methyl-1-butyl, 3-Methyl-1-butyl, 2-Methyl-2-butyl, 3-Methyl-2-butyl, 2,2-Dimethyl-1-propyl, 1-Hexyl, 2-Hexyl, 3-Hexyl, 2-Methyl-1-pentyl, 3-Methyl-1-pentyl, 4-Methyl-1-pentyl, 2-Methyl-2-pentyl, 3-Methyl-2-pentyl, 4-Methyl-2-pentyl, 2-Methyl-3-pentyl, 3-Methyl-3-pentyl, 2,2-Dimethyl-1-butyl, 2,3-Dimethyl-1-butyl, 3,3-Dimethyl-1-butyl, 2-Ethyl-1-butyl, 2,3-Dimethyl-2-butyl, 3,3-Dimethyl-2-butyl, 1-Heptyl, 1-Octyl, 1-Nonyl, 1-Decyl, 1-Undecyl, 1-Dodecyl, 1-Tetradecyl, 1-Hexadecyl, 1-Octadecyl, 2-Hydroxyethyl, Benzyl, 3-Phenylpropyl, 2-Cyanoethyl, 2-(Methoxycarbonyl)-ethyl, 2-(Ethoxycarbonyl)-ethyl, 2-(n-Butoxy-carbonyl)-ethyl, Trifluormethyl, Difluormethyl, Fluormethyl, Pentafluorethyl, Heptafluorpropyl, Heptafluorisopropyl, Nonafluorbutyl, Nonafluorisobutyl, Undecylfluorpentyl, Undecylfluorisopentyl, 6-Hydroxyhexyl und Propylsulfonsäure;
• • Glykole, Butylenglykole und deren Oligomere mit 1 bis 100 Einheiten und einem Wasserstoff oder einem C₁- bis C₈-Alkyl als Endgruppe, wie beispielsweise R^AO-(CHR^B-CH₂-O)_m-CHR^B-CH₂- Oder R^AO-(CH₂CH₂CH₂CH₂O)_m-CH₂CH₂CH₂CH₂- mit R^A und R^B bevorzugt Wasserstoff, Methyl oder Ethyl und n bevorzugt 0 bis 3, insbesondere 3-Oxabutyl, 3-Oxapentyl, 3,6-Dioxaheptyl, 3,6-Dioxaoctyl, 3,6,9-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9,12-Tetraoxatridecyl und 3,6,9,12-Tetraoxatetradecyl;
• • Vinyl;
• • 1-Propen-1-yl, 1-Propen-2-yl und 1-Propen-3-yl; und
• • N,N-Di-C₁-C₆-alkyl-amino, wie beispielsweise N,N-Dimethylamino und N,N-Diethylamino.

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

• • hydrogen;
• • straight-chain or branched, unsubstituted or mono- to polysubstituted by hydroxyl, halogen, phenyl, cyano, C ₁ -C ₆ -alkoxycarbonyl and / or SO ₃ H-substituted C ₁ -C ₁₈ -alkyl having a total of 1 to 20 carbon atoms, such as methyl , Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl 1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl , 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2 Methyl 3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1 -butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl , 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl l, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;
• Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C ₁ - to C ₈ -alkyl as an end group, such as R ^A O- (CHR ^B -CH ₂ -O) _m -CHR ^B -CH ₂ Or R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^B 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;
• • vinyl;
• 1-propen-1-yl, 1-propen-2-yl and 1-propen-3-yl; and
• N, N-di-C ₁ -C ₆ -alkyl-amino, such as N, N-dimethylamino and N, N-diethylamino.

Most preferably, the radicals R ¹ to R ⁹ independently of one another are hydrogen or C ₁ -C ₁₈ -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, for phenyl, for 2-hydroxyethyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N -Diethylamino, for chlorine and for CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - with m is 0 to 3.

• • einer der Reste R¹ bis R⁵ Methyl, Ethyl oder Chlor ist und die verbleibenden Reste R¹ bis R⁵ Wasserstoff sind;
• • R³ Dimethylamino ist und die verbleibenden Reste R¹, R², R⁴ und R⁵ Wasserstoff sind;
• • alle Reste R¹ bis R⁵ Wasserstoff sind;
• • R² Carboxy oder Carboxamid ist und die verbleibenden Reste R¹, R², R⁴ und R⁵ Wasserstoff sind; oder
• • R¹ und R² oder R² und R³ 1,4-Buta-1,3-dienylen ist und die verbleibenden Reste R¹, R², R⁴ und R⁵ Wasserstoff sind; und insbesondere solche, bei denen
• • R¹ bis R⁵ Wasserstoff sind; oder
• • einer der Reste R¹ bis R⁵ Methyl oder Ethyl ist und die verbleibenden Reste R¹ bis R⁵ Wasserstoff sind.

Very particular preference is given as Pyridiniumionen (IIIIa) such, 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 radicals 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.

When very particularly preferred pyridinium ions (IIIa) are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-tetra-decyl) -2-methyl-pyridinium, 1- (1-hexadecyl) -2-methyl-pyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1- (1-Butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium and 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-Tetradecyl) -2-methyl-3-ethylpyridinium and 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium.

• • R¹ bis R⁴ Wasserstoff sind; oder
• • einer der Reste R¹ bis R⁴ Methyl oder Ethyl ist und die verbleibenden Reste R¹ bis R⁴ Wasserstoff sind. Ganz besonders bevorzugt setzt man als Pyrimidiniumionen (IIIc) solche ein, bei denen
• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind; oder
• • R¹ Wasserstoff, Methyl oder Ethyl ist, R² und R⁴ Methyl sind und R³ Wasserstoff ist.

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

• • R ¹ to R ^{4 are} hydrogen; or
• • one of the radicals R ¹ to R ^{4 is} methyl or ethyl and the remaining radicals R ¹ to R ^{4 are} hydrogen. Very particularly preferred pyrimidinium ions (IIIc) are those in which
• • R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl; or
• • R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind;
• • R¹ Wasserstoff, Methyl oder Ethyl ist, R² und R⁴ Methyl sind und R³ Wasserstoff ist;
• • R¹ bis R⁴ Methyl sind; oder
• • R¹ bis R⁴ Methyl Wasserstoff sind.

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

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

• • R¹ Wasserstoff, Methyl, Ethyl, 1-Propyl, 1-Butyl, 1-Pentyl, 1-Hexyl, 1-Octyl, 1-Propen-3-yl, 2-Hydroxyethyl oder 2-Cyanoethyl und R² bis R⁴ unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind.

Very particularly preferred imidazolium ions (IIIe) are those in which

• R ^{1 is} hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 1-propen-3-yl, 2-hydroxyethyl or 2-cyanoethyl and R ² to R ⁴ independently of one another are hydrogen, methyl or ethyl.

When Very particularly preferred imidazolium ions (IIIe) may be mentioned 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methyl-imidazolium, 1- (1-hexyl) -3-ethyl-imidazolium, 1- (1-hexyl) -3-butyl-imidazolium, 1- (1-octyl) -3-methyl-imidazolium, 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, i- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-Tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butyl imidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium and 1- (prop-1-en-3-yl) -3-methylimidazolium.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred pyrazolium ions (IIIf), (IIIg) or (IIIg ') are those in which

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

• • R¹ bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind.
• Ganz besonders bevorzugt setzt man als 1-Pyrazoliniumionen (IIIi) solche ein, bei denen
• • unabhängig voneinander R¹ bis R⁶ Wasserstoff oder Methyl sind.

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

• • R ¹ to R ^{4 are} independently hydrogen or methyl.
• Very particular preference is given as 1-pyrazolinium (IIIi) such as those in which
• • independently of one another R ¹ to R ^{6 are} hydrogen or methyl.

• • R¹ Wasserstoff, Methyl, Ethyl oder Phenyl ist und R² bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

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

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

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Phenyl sind und R³ bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

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

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

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl, Ethyl, 1-Butyl oder Phenyl sind, R³ und R⁴ unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind und R⁵ und R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to imidazolinium ions (IIIl) which are those in which

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

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind und R³ bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using as imidazolinium ions (IIIm) or (IIIm ') 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.

• • R¹ bis R³ unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind und R⁴ bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using as imidazolinium ions (IIIn) or (IIIn ') 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.

• • R¹ Wasserstoff, Methyl, Ethyl oder Phenyl ist und R² und R³ unabhängig voneinander Wasserstoff oder Methyl sind.

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

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

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Phenyl sind und R³ Wasserstoff, Methyl oder Phenyl ist.

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

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

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² und R³ unabhängig voneinander Wasserstoff oder Methyl sind, oder R² und R³ zusammen 1,4-Buta-1,3-dienylen ist.

Very particular preference is given as 1,2,3-triazolium ions (IIIr), (IIIr ') or (IIIr'') such, in which

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

• • R¹ Wasserstoff, Methyl, Ethyl oder Phenyl ist und R² bis R⁹ unabhängig voneinander Wasserstoff oder Methyl sind.

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

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

• • R¹ und R⁴ unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Phenyl sind und R² und R³ sowie R⁵ bis R⁸ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred imidazolidinium ions (IIIt) are those in which

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

• • R¹ bis R³ unabhängig voneinander C₁-C₁₈-Alkyl sind; oder
• • R¹ und R² zusammen 1,5-Pentylen oder 3-Oxa-1,5-pentylen sind und R³ C₁-C₁₈-Alkyl, 2-Hydroxyethyl oder 2-Cyanoethyl ist.

Very particular preference is given to using as ammonium ions (IIIu) those in which

• • R ¹ to R ^{3 are} independently C ₁ -C ₁₈ alkyl; or
• • R ¹ and R ² together are 1,5-pentylene or 3-oxa-1,5-pentylene and R ^{3 is} C ₁ -C ₁₈ alkyl, 2-hydroxyethyl or 2-cyanoethyl.

When Very particularly preferred ammonium ions (IIIu) are methyltri (1-butyl) ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.

Examples of the tertiary amines of which the quaternary ammonium ions of the general For mel (IIIu) by quaternization with the radicals 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, di-isopropylethylamine, di-iso-propyl-n- propylamine, di-isopropylbutylamine, di-isopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, diisopropyl-2-ethylhexylamine, di-n-butylethylamine, di-n-butyl-n-propylamine, di-isopropyl 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-butyl 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 quaternary Ammonium ions of the general formula (IIIu) are those which are of following tertiary Derive amines by quaternization with the said radicals R, such as di-iso-propylethylamine, diethyl-tert-butylamine, di-isopropylbutylamine, Di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines from pentyl isomers.

Especially 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.

• • R¹ bis R⁵ Methyl sind.

Very particular preference is given to guanidinium ions (IIIv) as those in which

• • R ¹ to R ^{5 are} methyl.

When very particularly preferred guanidinium ion (IIIv) is N, N, N ', N', N ", N" -hexamethylguanidinium.

• • R¹ und R² unabhängig voneinander Methyl, Ethyl, 1-Butyl oder 1-Octyl sind und R³ Wasserstoff, Methyl, Ethyl, Acetyl, -SO₂OH oder -PO(OH)₂ ist;
• • R¹ Methyl, Ethyl, 1-Butyl oder 1-Octyl ist, R² eine -CH₂-CH₂-OR⁴-Gruppe ist und R³ und R⁴ unabhängig voneinander Wasserstoff, Methyl, Ethyl, Acetyl, -SO₂OH oder -PO(OH)₂ sind; oder
• • R¹ eine -CH₂-CH₂-OR⁴-Gruppe ist, R² eine -CH₂-CH₂-OR⁵-Gruppe ist und R³ bis R⁵ unabhängig voneinander Wasserstoff, Methyl, Ethyl, Acetyl, -SO₂OH oder -PO(OH)₂ sind.

Very particular preference is given to using as cholinium ions (IIIw) those in which

• • R ¹ and R ^{2 are} independently methyl, ethyl, 1-butyl or 1-octyl and R ^{3 is} hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ;
• • R ^{1 is} methyl, ethyl, 1-butyl or 1-octyl, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁴ group and R ³ and R ^{4 are} independently hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ; or
• • R ^{1 is} a -CH ₂ -CH ₂ -OR ⁴ group, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁵ group and R ³ to R ^{5 are} independently hydrogen, methyl, ethyl, acetyl, -SO _{2 are} OH or -PO (OH) ₂ .

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

• • R¹ bis R³ unabhängig voneinander C₁-C₁₈-Alkyl, insbesondere Butyl, Isobutyl, 1-Hexyl oder 1-Octyl sind.

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

• • R ¹ to R ^{3 are} independently C ₁ -C ₁₈ alkyl, especially butyl, isobutyl, 1-hexyl or 1-octyl.

Under the aforementioned heterocyclic cations are the pyridinium ions, Pyrazolinium-, pyrazolium ions and the imidazolinium- and the Imidazoliumionen preferred. Furthermore, ammonium ions are preferred.

Particularly preferred are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-Octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2- methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-Hexyl) -2-ethylpyridinium, 1- (1-Octyl) -2-ethylpyridinium, 1- (1-Dodecyl) -2-ethylpyridinium, 1- (1-Tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1- (1-butyl) -2-methyl-3-ethyl- pyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium, 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1- (1-dodecyl) -2-methyl- 3-ethyl-pyridinium , 1- (1-Tetradecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-hexade cyl) -2-methyl-3-ethylpyridinium, 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium , 1- (1-Tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- ( 1-hexyl) -3-methylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1 - (1-hexadecyl) -3-methylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1 - (1-hexyl) -2,3-dimethylimidazolium and 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3 ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1, 4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium and 1- (prop-1-ene -3-yl) -3-methylimidazolium.

When Anions are in principle all anions usable.

• • der Gruppe der Halogenide der Formel: F^–, Cl^–, Br^–, I^–
• • der Gruppe der halogenhaltigen Verbindungen und der Pseudohalogenide der Formel: BF₄ ^–, PF₆ ^–, CF₃SO₃ ^–, (CF₃SO₃)₂N^–, CF₃CO₂ ^–, CCl₃CO₂ ^–, CN^–, SCN^–, OCN^–
• • der Gruppe der Sulfate, Sulfite und Sulfonate der allgemeinen Formel: SO₄ ^2–, HSO₄ ^–, SO₃ ^2–, HSO₃ ^–, R^aOSO₃ ^–, R^aSO₃ ^–
• • der Gruppe der Phosphate der allgemeinen Formel PO₄ ^3–, HPO₄ ^2–, H₂PO₄ ^–, R^aPO₄ ^2–, HR^aPO₄ ^–, R^aR^bPO₄ ^–
• • der Gruppe der Phosphonate und Phosphinate der allgemeinen Formel: R^aHPO₃ ^–, R^aR^bPO₂ ^–, R^aR^bPO₃ ^–
• • der Gruppe der Phosphite der allgemeinen Formel: PO₃ ^3–, HPO₃ ^2–, H₂PO₃ ^–, R^aPO₃ ^2–, R^aHPO₃ ^–, R^aR^bPO₃ ^–
• • der Gruppe der Phosphonite und Phosphinite der allgemeinen Formel: R^aR^bPO₂ ^–, R^aHPO₂ ^–, R^aR^bPO^–, R^aHPO^–
• • der Gruppe der Carbonsäuren der allgemeinen Formel: R^aCOO^–
• • der Gruppe der Borste der allgemeinen Formel: BO₃ ^3–, HBO₃ ^2–, H₂BO₃ ^–, R^aR^bBO₃ ^–, R^aHBO₃ ^–, R^aBO₃ ^2–, B(OR^a)(OR^b)(OR^c)(OR^d)^–, B(HSO₄)^–, B(R^aSO₄)^–
• • der Gruppe der Boronate der allgemeinen Formel: R^aBO₂ ^2–, R^aR^bBO^–
• • der Gruppe der Silikate und Kieselsäuresäureester der allgemeinen Formel: SiO₄ ^4–, HSiO₄ ^3–, H₂SiO₄ ^2–, H₃SiO₄ ^–, R^aSiO₄ ^3–, R^aR^bSiO₄ ^2–, R^aR^bR^cSiO₄ ^–, HR^aSiO₄ ^2–, H₂R^aSiO₄ ^–, HR^aR^bSiO₄ ^–
• • der Gruppe der Alkyl- bzw. Arylsilan-Salze der allgemeinen Formel: R^aSiO₃ ^3–, R^aR^bSiO₂ ^2–, R^aR^bR^cSiO^–, R^aR^bR^cSiO₃ ^–, R^aR^bR^cSiO₂ ^–, R^aR^bSiO₃ ^2–
• • der Gruppe der Carbonsäureimide, Bis(sulfonyl)imide und Sulfonylimide der allgemeinen Formel:
  
• • der Gruppe der Methide der allgemeinen Formel:
  

The anion [Y] ^{n of} the ionic liquid is for example selected from

• • the group of halides of the formula: F ^- , Cl ^- , Br ^- , I ^-
• The group of halogen-containing compounds and pseudohalides of the formula: BF ₄ ^- , PF ₆ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₃ ) ₂ N ^- , CF ₃ CO ₂ ^- , CCl ₃ CO ₂ ^- , CN ^- , SCN ^- , OCN ^-
• • the group of sulfates, sulfites and sulfonates of the general formula: SO ₄ ^2- , HSO ₄ ^- , SO ₃ ^2- , HSO ₃ ^- , R ^a OSO ₃ ^- , R ^a SO ₃ ^-
• • the group of phosphates of the general formula PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^-
• The group of phosphonates and phosphinates of the general formula: R ^a HPO ₃ ^- , R ^a R ^b PO ₂ ^- , R ^a R ^b PO ₃ ^-
• The group of phosphites of the general formula: PO ₃ ^3- , HPO ₃ ^2- , H ₂ PO ₃ ^- , R ^a PO ₃ ^2- , R ^a HPO ₃ ^- , R ^a R ^b PO ₃ ^-
• The group of phosphonites and phosphinites of the general formula: R ^a R ^b PO ₂ ^- , R ^a HPO ₂ ^- , R ^a R ^b PO ^- , R ^a HPO ^-
• • the group of carboxylic acids of the general formula: R ^a COO ^-
• • the group of bristles of the general formula: BO ₃ ^3- , HBO ₃ ^2- , H ₂ BO ₃ ^- , R ^a R ^b BO ₃ ^- , R ^a HBO ₃ ^- , R ^a BO ₃ ^2- , B (OR ^a ) (OR ^b ) (OR ^c ) (OR ^d ) ^- , B (HSO ₄ ) ^- , B (R ^a SO ₄ ) ^-
• The group of boronates of the general formula: R ^a BO ₂ ^2- , R ^a R ^b BO ^-
• 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 ^a SiO ₄ ^3- , R ^a R ^b SiO ₄ ^2- , R ^a R ^b R ^c SiO ₄ ^- , HR ^a SiO ₄ ^2- , H ₂ R ^a SiO ₄ ^- , HR ^a R ^b SiO ₄ ^-
• • the group of alkylsilane and arylsilane salts of the general formula: R ^a SiO ₃ ^3-, R ^a R ^b SiO ₂ ^2-, R ^a R ^b R ^c SiO ^-, R ^a R ^b R ^c SiO ₃ ^-, R ^a R ^b R ^c SiO ₂ ^- , R ^a R ^b SiO ₃ ^2-
• The group of the carboxylic imides, bis (sulfonyl) imides and sulfonyl imides of the general formula:
  
• The group of methides of the general formula:
  

In this R ^a , R ^b , R ^c and R ^d are each independently hydrogen, C ₁ -C ₃₀ -alkyl, optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C C ₂ -C ₁₈ -alkyl, C ₆ -C ₁₄ -aryl, C ₅ -C ₁₂ -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, two of them together having one unsaturated, saturated or aromatic, given where appropriate, by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups interrupted ring, said radicals each additionally by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or Heterocycles may be substituted.

Therein, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, substituted C ₁ -C ₁₈ -alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3, 3-tetramethylbutyl, benzyl, 1-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1, 3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2 -chloroethyl, 2-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.

Optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C ₁₈ alkyl interrupted are, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxa nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4- oxaheptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3- oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8, 12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl.

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

The Number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited or limited automatically by the size of the rest or the ring module. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or especially preferably not more than 3. Furthermore, there are between two Heteroatoms usually at least one, preferably at least two Carbon atom (s).

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

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

Optionally C ₆ -C ₁₄ -aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles are, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, Dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2 , 4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl.

Optionally C ₅ -C ₁₂ -cycloalkyl which is substituted by functional groups, aryl, alkyl, aryloxy, halogen, heteroatoms and / or heterocycles are, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

One five to six-membered, oxygen, nitrogen and / or sulfur atoms heterocycle having, for example, furyl, thiophenyl, Pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, Benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, Methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, Isopropylthiophenyl or tert-butylthiophenyl.

Preferred anions are selected from the group of halides, the group of halogen-containing compounds and pseudohalides, the group of sulfates, sulfites and sulfonates, the group of phosphates, and the group of carboxylic acids, in particular from the group of halides, the group of halogen-containing compounds and the pseudohalogens, the group of carboxylic acids, the group containing SO ₄ ^2- , SO ₃ ^2- , R ^a OSO ₃ ^- and R ^a SO ₃ ^- , and the group containing PO ₄ ^3- and R ^a R ^b PO ₄ ^- .

Preferred anions are in particular chloride, bromide, iodide, SCN ^-, OCN ^-, CN ^-, acetate, propionate, benzoate, C ₁ -C ₄ alkyl sulfates, R ^a -COO ^-, R ^a SO ₃ ^-, R ^a R ^b PO ₄ ^- , methanesulfonate, tosylate or di- (C ₁ -C ₄ -alkyl) phosphates.

Particularly preferred anions are Cl ^- , CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O) ₂ PO ₂ ^- .

In a further preferred embodiment, ionic liquids of the formula I with
[A] _n ⁺ 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium , 1- (1-Hexyl) -3-methyl-imidazolium, 1- (1-hexyl) -3-ethyl-imidazolium, 1- (1-hexyl) -3-butyl-imidazolium, 1- (1-octyl) 3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3 ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium , 1- (1-Tetradecyl) -3-butylimidazolium, 1- (1-Tetradecyl) -3-octylimidazolium, 1- (1-Hexadecyl) -3-methylimidazolium, 1- (1-Hexadecyl) -3-ethylimidazolium, 1 - (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dim ethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4- Dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1, 3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium or 1- (Prop-1 -en-3-yl) -3-methylimidazolium; and
[Y] ^{n +} Cl ^- , CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O) ₂ PO ₂ ^- ;
used.

In a further particularly preferred embodiment, ionic liquids are used whose anions are selected from the group of halogen-containing compounds and pseudohalogens, the group of sulfates, sulfites and sulfonates, the group of phosphates, and the group of carboxylic acids, in particular from the group of carboxylic acids containing the group containing SO ₄ ^2- , SO ₃ ^2- , R ^a OSO ₃ ^- and R ^a SO ₃ ^- , and the group containing PO ₄ ^3- and R ^a R ^b PO ₄ ^- .

Preferred anions are in particular SCN ^-, OCN ^-, CN ^-, acetate, propionate, benzoate, C ₁ -C ₄ alkyl sulfates, R ^a -COO ^-, R ^a SO ₃ ^-, R ^a R ^b PO ₄ ^-, methanesulfonate, tosylate or di (C ₁ -C ₄ alkyl) phosphates.

Particularly preferred anions are CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O) ₂ PO ₂ ^- ,

In a further particularly preferred embodiment, ionic liquids of the formula I with
[A] _n ⁺ 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1 -Hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-Octyl) -3-butylimidazolium, 1- (1-Dodecyl) -3-methylimidazolium, 1- (1-Dodecyl) -3-ethylimidazolium, 1- (1-Dodecyl) -3-butylimidazolium, 1- (1 Dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl ) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) - 3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) - 2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazo Iium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-one ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium or 1- (prop-1-en-3-yl) -3-methylimidazolium; and
[Y] ^{n +} CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O) ₂ PO ₂ ^- ;
used.

In Another particularly preferred embodiment is ionic liquids used, their anions selected are from the group of halides.

preferred Anion is especially chloride.

In a further particularly preferred embodiment, ionic liquids of the formula I with
[A] _n ⁺ 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium , 1- (1-Hexyl) -3-methyl-imidazolium, 1- (1-hexyl) -3-ethyl-imidazolium, 1- (1-hexyl) -3-butyl-imidazolium, 1- (1-octyl) 3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3 ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium , 1- (1-Tetradecyl) -3-butylimidazolium, 1- (1-Tetradecyl) -3-octylimidazolium, 1- (1-Hexadecyl) -3-methylimidazolium, 1- (1-Hexadecyl) -3-ethylimidazolium, 1 - (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-di methylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4- Dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1, 3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium or 1- (Prop-1 -en-3-yl) -3-methylimidazolium; and
[y] ^{n +} Cl ^- ;
used.

In a further preferred embodiment, ionic liquids are used whose anions are selected from the group comprising HSO ₄ ^- , HPO ₄ ^2- , H ₂ PO ₄ ^- and HR ^a PO ₄ ^- ; especially HSO ₄ ^- .

In particular, ionic liquids of formula I with
[A] _n ⁺ 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium , 1- (1-Hexyl) -3-methyl-imidazolium, 1- (1-hexyl) -3-ethyl-imidazolium, 1- (1-hexyl) -3-butyl-imidazolium, 1- (1-octyl) 3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3 ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium , 1- (1-Tetradecyl) -3-butylimidazolium, 1- (1-Tetradecyl) -3-octylimidazolium, 1- (1-Hexadecyl) -3-methylimidazolium, 1- (1-Hexadecyl) -3-ethylimidazolium, 1 - (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dim ethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4- Dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1, 3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium or 1- (Prop-1 -en-3--yl) -3-methylimidazolium; and
[Y] ^{n +} HSO ₄ ^- ;
used.

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

In a further embodiment of the invention Is it possible an ionic liquid of formula II or a mixture of ionic liquids of formula II, preferably becomes an ionic liquid of the formula II used.

In a further embodiment of the invention Is it possible a mixture of ionic liquids of formulas I and II.

In the method according to the invention in step A) the targeted degradation of the cellulose in the presence of a Acid, if appropriate with addition of water (step A1) or at elevated temperature, optionally in the presence of water (step A2).

In Step A1 can as acids inorganic acids, organic acids or mixtures thereof.

Examples of inorganic acids are hydrogen halide acids, such as HF, HCl, HBr or Hl, perhalogenic acids such as HClO ₄ , halogen acids such as HClO ₃ , sulfur-containing acids such as H ₂ SO ₄ , polysulfuric acid or H ₂ SO ₃ , nitrogen-containing acids , such as HNO ₃ , or phosphorus-containing acids, such as H ₃ PO ₄ , polyphosphoric acid or H ₃ PO ₃ . Preference is given to using hydrohalic acids, such as, for example, HCl or HBr, H ₂ SO ₄ , HNO ₃ or H ₃ PO ₄ , in particular HCl, H ₂ SO ₄ or H ₃ PO ₄ .

• • C₁-C₆-Alkancarbonsäuren, beispielsweise Essigsäure, Propionsäure, n-Butancarbonsäure oder Pivalinsäure,
• • Di- bzw. Polycarbonsäuren, beispielsweise Bernsternsäure, Maleinsäure oder Fumarsäure,
• • Hydroxycarbonsäuren, beispielsweise Hydroxyessigsäure, Milchsäure, Äpfelsäure oder Citronensäure,
• • halogenierte Carbonsäuren, beispielsweise C₁-C₆-Halogenalkancarbonsäuren, z.B. Fluoressigsäure, Chloressigsäure, Bromessigsäure, Difluoressigsäure, Dichloressigsäure, Chlorfluoressigsäure, Trifluoressigsäure, Trichloressigsäure, 2-Chlorpropionsäure, Perfluorpropionsäure oder Perfluorbutancarbonsäure,
• • aromatische Carbonsäuren, beipielsweise Arylcarbonsäuren, wie Benzoesäure; oder Sulfonsäuren, wie
• • C₁-C₆-Alkansulfonsäuren, beispielsweise Methansulfonsäure oder Ethansulfonsäure,
• • halogenierte Sulfonsäuren, beispielsweise C₁-C₆-Halogenalkansulfonsäuren, wie Trifluormethansulfonsäure,
• • aromatische Sulfonsäuren, beispielsweise Arylsulfonsäuren, wie Benzolsulfonsäure oder 4-Methylphenylsulfonsäure.

Examples of organic acids are carboxylic acids, such as

• C ₁ -C ₆ -alkanecarboxylic acids, for example acetic acid, propionic acid, n-butanecarboxylic acid or pivalic acid,
• Di- or polycarboxylic acids, for example succinic acid, maleic acid or fumaric acid,
• Hydroxycarboxylic acids, for example hydroxyacetic acid, lactic acid, malic acid or citric acid,
• Halogenated carboxylic acids, for example C ₁ -C ₆ -haloalkanecarboxylic acids, for example fluoroacetic acid, chloroacetic acid, bromoacetic acid, difluoroacetic acid, dichloroacetic acid, chlorofluoroacetic acid, trifluoroacetic acid, trichloroacetic acid, 2-chloropropionic acid, perfluoropropionic acid or perfluorobutanecarboxylic acid,
• Aromatic carboxylic acids, for example arylcarboxylic acids, such as benzoic acid; or sulfonic acids, such as
• C ₁ -C ₆ -alkanesulfonic acids, for example methanesulfonic acid or ethanesulfonic acid,
• Halogenated sulfonic acids, for example C ₁ -C ₆ -haloalkanesulfonic acids, such as trifluoromethanesulfonic acid,
• Aromatic sulfonic acids, for example arylsulfonic acids, such as benzenesulfonic acid or 4-methylphenylsulfonic acid.

C ₁ -C ₆ -alkanecarboxylic acids, for example acetic acid or propionic acid, halogenated carboxylic acids, for example C ₁ -C ₆ -haloalkanecarboxylic acids, eg. Fluoroacetic acid, chloroacetic acid, difluoroacetic acid, dichloroacetic acid, chlorofluoroacetic acid, trifluoroacetic acid, trichloroacetic acid or perfluoropropionic acid, or sulfonic acids such as C ₁ -C ₆ -alkanesulfonic acids, for example methanesulfonic acid or ethanesulfonic acid, halogenated sulfonic acids, for example C ₁ -C ₆ -haloalkanesulfonic acids, such as trifluoromethanesulfonic acid, or arylsulfonic acids, such as benzenesulfonic acid or 4-methylphenylsulfonic acid. Preferably, acetic acid, chlorofluoroacetic acid, trifluoroacetic acid, perfluoropropionic acid, methanesulfonic acid, trifluoromethanesulfonic acid or 4-methylphenylsulfonic acid are used.

In a particular embodiment of the invention be called acid Sulfuric acid, Acetic acid, trifluoroacetic, methane or 4-methylphenyl sulfonic acid used. For the case where 4-methylphenyl sulfonic acid monohydrate is used, is already an equivalent Water with in front.

In a particular embodiment become ionic liquids and acids used, whose anions are identical. Preferably, these are Anions acetate, trifluoroacetate, chloride or bromide; especially preferably acetate; also particularly preferred chloride.

In another particular embodiment become ionic liquids and acids used, whose anions are not identical.

In Step B uses acylating agents. acylating For the purposes of the present invention are carboxylic acid derivatives and ketenes and Diketenes.

wobei die Reste folgende Bedeutung haben:
R^x, R^x' H, C₁-C₃₀-Alkyl, C₂-C₃₀-Alkenyl, C₂-C₃₀-Alkinyl, C₃-C₁₂-Cycloalkyl, C₅-C₁₂-Cycloalkenyl, Aryl oder Heterocyclyl, wobei diese sieben letztgenannten Reste ggf. substituiert sein können;
X Halogen, Imidazol-1-yl oder O-COR^x'.Carboxylic acid derivatives in the context of the present invention are carboxylic acid derivatives of the formula IV

where the radicals have the following meaning:
R ^x , R ^{x 'is} H, C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, C ₂ -C ₃₀ -alkynyl, C ₃ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkenyl, aryl or Heterocyclyl, where these seven latter radicals may be optionally substituted;
X is halogen, imidazol-1-yl or O-COR ^{x '} .

wobei die Reste folgende Bedeutung haben:
R^y, R^y', R^z, R^z' Wasserstoff, C₁-C₃₀-Alkyl, C₂-C₃₀-Alkenyl, C₂-C₃₀-Alkinyl, C₃-C₁₂-Cycloalkyl, C₅-C₁₂-Cycloalkenyl, Aryl oder Heterocyclyl, wobei die sieben letztgenannten Reste ggf. substituiert sein können;
oder
R^y und R^z bzw. R^y' und R^z' bilden gemeinsam eine ggf. substituierte -Y_o-(CH₂)_p-, -(CH₂)_q-Y-(CH₂)_r- oder eine -CH=CH-CH=CH- -Kette, wobei
Y O, S, S(=O), S(=O)₂, NH oder NC₁-C₆-Alkyl;
o 0 oder 1;
p 2, 3, 4, 5, 6, 7 oder 8;
q, r 1,2, 3, 4, 5 oder 6;
bedeuten.Ketenes for the purposes of the present invention (compounds of the formula V) are ketenes of the formula Va and diketene in the sense of the present invention are diketenes of the formula Vb1 or mixed diketenes of the formula Vb2,

where the radicals have the following meaning:
R ^y , R ^{y '} , R ^z , R ^{z' are} hydrogen, C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, C ₂ -C ₃₀ -alkynyl, C ₃ -C ₁₂ -cycloalkyl, C ₅ - C ₁₂ -cycloalkenyl, aryl or heterocyclyl, where the seven last-mentioned radicals may optionally be substituted;
or
R ^y and R ^z and R ^{y '} and R ^z' together form an optionally substituted -Y _o - (CH ₂ ) _p -, - (CH ₂ ) _q -Y- (CH ₂ ) _r - or a -CH = CH-CH = CH- chain, where
YO, S, S (= O), S (= O) ₂ , NH or NC ₁ -C ₆ alkyl;
o is 0 or 1;
p is 2, 3, 4, 5, 6, 7 or 8;
q, r is 1,2, 3, 4, 5 or 6;
mean.

As optionally substituted C ₁ -C ₃₀ -alkyl radicals for R ^x , R ^{x '} , R ^y , R ^y' , R ^z or R ^{z '} are in particular unsubstituted C ₁ -C ₃₀ -alkyl radicals or by functional groups , Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C ₁ -C ₃₀ -alkyl radicals,
preferably C ₁ -C ₃₀ -alkyl radicals, such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1 Pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1 -propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl 2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3 , 3-Dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4 Trimethylpentyl, 1,1,3,3-tetramethylbutyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1 Octadecyl and 1-eicosan-yl, more preferably methyl, ethyl, 1-propyl, 1-butyl, 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl; or
preferably C ₁ -C ₃₀ -alkyl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, methoxycarbonylmethyl, 2-methoxycarbonylethyl , Ethoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2- (butoxycarbonyl) -ethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, formyl, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl , 6-hydroxyhexyl, 2-hydroxy-2,2-dimethylethyl, aminomethyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, methylaminomethyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl , 4-methylaminobutyl, 6-methylaminohexyl, dimethylaminomethyl, 2-dimethylaminoethyl, 2-dimethylamino-propyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, phenoxymethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypro pyl, 4-phenoxybutyl, 6-phenoxyhexyl, methoxymethyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, ethoxymethyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, 2-butoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, dimethoxymethyl, diethoxymethyl, 2,2-diethoxymethyl, 2,2-diethoxyethyl, acetyl, propionyl, C _m F _{2 (m A) + (1-b)} H _{2a + b} with m equal to 1 to 30, 0 ≤ a ≤ m and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C _{(m - 2)} F _{2 (m - 2) + 1} , C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ ), chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl-2-chloroethyl , Methylthiomethyl, ethylthiomethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa-octyl, 11-hydroxy-3,6,9-trioxa-undecyl , 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy -5,10-dioxa-tetr adecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11- Methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3- oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

As optionally substituted C ₂ -C ₃₀ alkenyl radicals for R ^x , R ^{x '} , R ^y , R ^y' , R ^z or R ^{z '} are in particular unsubstituted C ₂ -C ₃₀ alkenyl radicals or by functional groups , Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C ₂ -C ₃₀ -alkenyl radicals,
preferably C ₂ -C ₃₀ -alkenyl radicals, such as, for example, vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl or trans-2-butenyl, particularly preferably vinyl or 2-propenyl; or
preferably C ₂ -C ₃₀ -alkenyl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, C _m F _{2 (m-a) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

As optionally substituted C ₂ -C ₃₀ -alkynyl radicals for R ^x , R ^{x '} , R ^y , R ^y' , R ^z or R ^{z '} are in particular unsubstituted C ₂ -C ₃₀ -alkynyl radicals or by functional groups , Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C ₂ -C ₃₀ -alkynyl radicals,
preferably C ₂ -C ₃₀ -alkynyl radicals, such as, for example, ethynyl, 1-propyn-3-yl, 1-propyn-1-yl or 3-methyl-1-propyn-3-yl, particularly preferably ethynyl or 1-propyne -3-yl.

As optionally substituted C ₃ -C ₁₂ -cycloalkyl radicals for R ^x , R ^{x '} , R ^y , R ^y' , R ^z or R ^{z '} are in particular unsubstituted C ₃ -C ₈ -cycloalkyl radicals or by funktionel le Called C ₃ -C ₁₂ -cycloalkyl radicals substituted by groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles,
preferably C ₃ -C ₁₂ -cycloalkyl radicals, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl or butylcyclohexyl, and also bicyclic systems such as norbornyl, preferably cyclopentyl or cyclohexyl;
or
preferably C ₃ -C ₁₂ -cycloalkyl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F _{2 (m - a) - (1 - b)} H _{2a - b} with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

As optionally substituted C ₅ -C ₁₂ -cycloalkenyl radicals for R ^x , R ^{x '} , R ^y , R ^y' , R ^z and R ^{z '} are in particular unsubstituted C ₃ -C ₈ cycloalkenyl radicals or by functional groups , Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles called C ₃ -C ₈ cycloalkenyl radicals, preferably C ₃ -C ₈ cycloalkenyl radicals, such as 3-cyclopentenyl, 2-cyclohexenyl , 3-cyclohexenyl, 2,5-cyclohexadienyl, as well as bicyclic system such as norbornyl, more preferably 3-cyclopentenyl, 2-cyclohexenyl or 3-cyclohexenyl;
or
preferably by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted C ₃ -C ₈ -cycloalkenyl radicals, such as C _n F _{2 (m - a) - 3 (1 - b )} H _{2a - 3b} with m ≤ 12, 0 ≤ a ≤ m and b = 0 or 1.

Unsubstituted C ₆ -C ₁₂ -aryl radicals or by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, ^as unsubstituted or substituted aryl radicals for R ^x , R ^{x '} , R ^y , R ^y' , R ^z are particularly Called halogen, heteroatoms and / or heterocycles substituted C ₆ -C ₁₂ -aryl radicals,
preferably C ₆ -C ₁₂ -aryl radicals, such as, for example, phenyl, α-naphthyl or β-naphthyl, particularly preferably phenyl;
or
preferably C ₆ -C ₁₂ -aryl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as tolyl, xylyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso -propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl , 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl , Isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _(5-a) H _a with 0 ≤ a ≤ 5, more preferably 4-tolyl.

Examples of optionally substituted heterocyclyl radicals which may be mentioned are unsubstituted heteroaryl radicals or heteroaryl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles,
preferably 5- or 6-membered heteroaryl radicals which have oxygen, nitrogen and / or sulfur atoms, such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl or benzothiazolyl;
or
preferably 5- or 6-membered heteroaryl radicals which contain oxygen, nitrogen and / or sulfur atoms, such as methylpyridy, dimethylpyridyl, Methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, chloropyridyl, or difluoropyridyl.

If R ^y and R ^z or R ^{y '} and R ^z' together represent an optionally substituted -Y _o - (CH ₂ ) _p -, - (CH ₂ ) _q -Y- (CH ₂ ) _r - or a -CH = CH-CH = CH- chain, are preferably a -Y _o - (CH ₂ ) _p -, - (CH ₂ ) _q -Y- (CH ₂ ) _r - or a -CH = CH-CH = CH - chain, especially - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ - or -CH = CH-CH = CH-, in particular - (CH ₂ ) ₅ - or - (CH ₂ ) ₆ - into consideration .
or
a C ₁ -C ₄ alkyl-substituted -Y _o - (CH ₂ ) _p -, - (CH ₂ ) _q -Y- (CH ₂ ) _r - or a C ₁ -C ₄ alkyl-substituted - CH = CH-CH = CH- chain, into consideration.

In an embodiment The present invention uses carboxylic acid derivatives of the formula IV.

In particular, carboxylic acid derivatives of the formula IV are used, where the radicals have the following meanings:
R ^x , R ^{x 'are} hydrogen or C ₁ -C ₃₀ alkyl;
X is halogen or O-COR ^{x '} .

Particular preference is given to using carboxylic acid derivatives of the formula IV where the radicals have the following meanings:
R ^{x is} hydrogen or C ₁ -C ₁₈ -alkyl, preferably hydrogen or C ₁ -C ₆ -alkyl; particularly preferably methyl, ethyl or butyl;
X is halogen, preferably chloride.

Equally particularly preferably, carboxylic acid derivatives of the formula IV are used, the radicals having the following meanings:
R ^{x is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
X is halogen, preferably chloride.

Particular preference is given to using carboxylic acid derivatives of the formula IV where the radicals have the following meanings:
R ^x , R ^{x 'are} hydrogen or C ₁ -C ₁₈ -alkyl, preferably hydrogen or C ₁ -C ₆ -alkyl; particularly preferably methyl, ethyl or butyl;
X OCOR ^{x '} .

Extraordinary preference is given to using carboxylic acid derivatives of the formula IV where the radicals R ^x and R ^{x 'have} the same meaning ("symmetrical carboxylic acid anhydrides").

Equally particularly preferably, carboxylic acid derivatives of the formula IV are used, the radicals having the following meanings:
R ^{x is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
X OCOR ^x .

Extraordinary preference is given to using carboxylic acid derivatives of the formula IV where the radicals R ^x and R ^{x 'have} the same meaning ("symmetrical carboxylic acid anhydrides").

In a further embodiment The present invention uses ketenes of the formula Va.

In particular, ketenes of the formula Va are used, where the radicals have the following meanings:
R ^{y is} hydrogen or C ₁ -C ₁₈ -alkyl, preferably hydrogen or C ₁ -C ₆ -alkyl; particularly preferably hydrogen, methyl or ethyl; most preferably hydrogen;
R ^{z is} hydrogen.

Likewise, in particular, ketenes of the formula Va are used, where the radicals have the following meanings:
R ^{y is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
R ^{z is} hydrogen.

In a further embodiment The present invention uses diketenes of the formula Vb1.

In particular, diketenes of the formula Vb1 are used, where the radicals have the following meanings:
R ^{y is} hydrogen or C ₁ -C ₁₈ -alkyl, preferably hydrogen or C ₁ -C ₆ -alkyl, particularly preferably hydrogen, methyl or ethyl, in particular hydrogen;
R ^{z is} hydrogen.

Likewise particularly preferred are diketenes of the formula Vb1, where the radicals have the following meanings:
R ^{y is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
R ^{z is} hydrogen.

In a further embodiment In the present invention, mixed diketenes of formula Vb2 used.

In particular, mixed diketenes of the formula Vb2 are used, where the radicals have the following meanings:
R ^y , R ^{y are} hydrogen or C ₁ -C ₆ -alkyl, preferably hydrogen, methyl or ethyl, in particular hydrogen;
R ^z , R ^{z 'is} hydrogen.

Likewise, in particular diketenes of the formula Vb2 be used, where the radicals have the following meanings:
R ^y , R ^{y 'is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl
R ^z , R ^{z 'is} hydrogen.

For the inventive method can Celluloses from a variety of sources are used such as. made of cotton, flax, ramie, straw, bacteria etc., or made of wood or bagasse, in the cellulose-enriched form.

In the inventive method But not only cellulose can be used, but in general a polysaccharide or an oligosaccharide. As examples of polysaccharides In addition to cellulose and hemicellulose, starch, glycogen, dextran and To call Tunicin. Likewise count For this purpose, the polycondensates of D-fructose, such as inulin, and u.a. Chitin and alginic acid. The corresponding versions apply here accordingly.

In an embodiment The present invention is a process according to the invention Polysaccharide, e.g. Cellulose, hemicellulose, starch, glycogen, Dextran, tunicin, inulin, chitin or alginic acid, preferably cellulose, implemented.

at the method according to the invention becomes a solution of cellulose in ionic liquid, produced. The concentration of cellulose can be in large areas be varied. Usually it is in the range of 0.1 to 50 wt .-%, based on the total weight the solution, preferably at 0.2 to 40 wt .-%, particularly preferably 0.3 to 30 wt .-% and particularly preferably at 0.5 to 20% wt .-%.

This solution process can be carried out at room temperature or under heating, but above the melting or softening temperature of the ionic Liquid, usually at a temperature of 0 to 200 ° C, preferably at 20 to 180 ° C, especially preferably at 50 to 150 ° C. It is also possible the dissolution process by intensive stirring or mixing and by entry of microwave or ultrasonic energy or by speeding up their combination.

These solution is now used in step A1) or in step A2).

In the step according to the invention A1) is the targeted degradation in the presence of an acid, optionally with the addition of Water performed.

When acids become inorganic acids, organic acids or mixtures thereof, as described above.

In a particular embodiment become ionic liquids and acids used, whose anions are identical. Preferably, these are Anions acetate, trifluoroacetate, chloride or bromide.

In another particular embodiment become ionic liquids and acids used, whose anions are not identical.

As already described above, the cellulose is in the ionic liquid solved. To this solution thus obtained will now be the acid and optionally water added. The addition of water may be necessary be when the adhering to the cellulose used water is not enough, the desired Achieve degree of degradation. In general, the proportion of water is the usual Cellulose in the range of 5 to 10 wt .-%, based on the total weight the cellulose used (cellulose per se + adherent water). For one Partial degradation of the cellulose will be stoichiometric necessary amounts of water and acid are added, necessary are to achieve a corresponding DP value. It is also possible Water and acid to use in excess and stop the reaction when the desired degree of degradation reaches is.

In another embodiment become the ionic liquid, Acid and if necessary pre-mixed with water and the cellulose dissolved in this mixture.

It there is also the possibility that one or more other solvents be added to the reaction mixture or already with the ionic liquid and / or the acid and / or possibly added to the water become. As a solvent come here in question, which is not the solubility of cellulose adversely affect like aprotic-dipolar solvents, for example, dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.

In a particular embodiment contains the reaction mixture is less than 5% by weight, preferably less than 2% by weight, in particular less than 0.1% by weight, of further solvents, based on the total weight of the reaction mixture.

The Hydrolysis becomes dependent of the ionic liquid and acid used at a temperature of the melting point of the ionic liquid up to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C carried out.

Usually the reaction takes place at ambient pressure. It may be case by case but also be advantageous in case of overpressure to work, especially if volatile acids are used.

As a rule, the reaction is carried out in air. But it is also possible under inert gas, so for example, under N ₂ , to work a noble gas or a mixture thereof.

Depending on the desired degree of degradation, the amount of acid used, the water to be added if necessary, in each case in relation to the cellulose used, the reaction time and possibly the Re set reaction temperature.

If it is desired to convert the cellulose, which is composed on average of x anhydroglucose units, into a cellulose whose number of anhydroglucose units is less than x, the amount of water used and acid used is usually adjusted according to the _{degree of} degradation (n _{anhydroglucose units} / n _Acid > 1). The greater the quotient n _{anhydroglucose units} / n _acid , the lower will be the average degradation of cellulose under otherwise identical reaction conditions and the same reaction time. The larger the quotient n _{anhydroglucose units} / n of _water , the lower will be the average degradation of cellulose under otherwise identical reaction conditions and the same reaction time.

It is possible, too to stop the hydrolysis reaction when the desired level of degradation is reached is by the acid intercepted with a base. Suitable bases are both inorganic Bases, e.g. Alkali hydroxides, carbonates, bicarbonates, but also organic bases such as e.g. Amines in stoichiometric relationship to the acid or in excess be used. In a further embodiment, as the base Hydroxide can be used, which is characterized in that whose cation corresponds to that of the ionic liquid used.

It is possible, too, to stop the degradation reaction when the desired degree of degradation has been reached, by adding appropriate amounts of acylating agent, which react with the remaining water.

These so obtained solution will now be used in step B).

alternative to step A1), step A2) can also be carried out.

In the step according to the invention A2), the cellulose is optionally with the addition of water at elevated temperature treated.

If ionic liquids are used, which have no acidic character, then will the degradation usually at temperatures of 50 ° C up to 200 ° C, preferably from 80 to 180 ° C, in particular from 50 to 150 ° C carried out.

Suitable ionic liquids are those whose anions are selected from the group of halides, the group of halogen-containing compounds, the group of carboxylic acids, the group containing SO ₄ ^2- , SO ₃ ^2- , R ^a OSO ₃ ^- OSO ₃ ^- and R ^a SO ₃ ^- , and the group containing PO ₄ ^3- and R ^a R ^b PO ₄ ^- . Preferred anions here are chloride, bromide, iodide, SCN ^-, OCN ^-, CN ^-, acetate, C ₁ -C ₄ alkyl sulfates, R ^a -COO ^-, R ^a SO ₃ ^-, R ^a R ^b PO ₄ ^-, methanesulfonate , Tosylate or C ₁ -C ₄ dialkyl phosphates; and particularly preferred anions are Cl ^- , CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O) ₂ PO ₂ ^- .

If ionic liquids are used which have acidic character, then it is also possible to lower the reaction temperature. Particular preference is given here to ionic liquids whose anions are selected from the group comprising HSO ₄ ^- , HPO ₄ ^2- , H ₂ PO ₄ ^- and HR ^a PO ₄ ^- ; especially HSO ₄ ^- .

Preferably become reactions in these ionic liquids at a temperature from 0 to 150 ° C, preferably from 20 to 150 ° C, in particular from 50 to 150 ° C carried out.

In an embodiment be the preparation of the reaction solution and the degradation in the same temperature.

In In another embodiment, the preparation of the reaction solution and the degradation is carried out at different temperatures.

From Case by case, it is also possible that already during the preparation of the reaction solution a degradation of cellulose takes place. In a special embodiment find the solution and the degradation process takes place in parallel, as it were.

As a rule, the reaction is carried out in air. But it is also possible under inert gas, so for example, under N ₂ , a noble gases or mixtures thereof, to work.

In dependence from the desired Degree of degradation, the reaction time and the reaction temperature is set.

In an embodiment Water is added, preferably in substoichiometric amounts, or it will be a surplus used on water and the reaction is stopped.

If the degradation is carried out in the presence of water it is possible the ionic liquid and Pre-mix the water and add the cellulose in this mixture to solve. It is also possible the water to the solution of ionic liquid and cellulose.

If it is desired to convert the cellulose, which is composed on average of x anhydroglucose units, into a cellulose whose number of anhydroglucose units is less than x, the amounts of water used are usually adjusted according to the _{degree of} degradation (n _{anhydroglucose units} / n _water > 1) ). The larger the quotient n _{anhydroglucose units} / n of _water , the lower will be the average degradation of cellulose under otherwise identical reaction conditions and the same reaction time and the higher the DP of the degraded cellulose (which of course will be smaller than the DP of the cellulose used).

In another embodiment is worked without the addition of water.

It there is also the possibility that one or more other solvents to the reaction mixture or the water - as far as this was added - are added. As a solvent come here in question, which is not the solubility of cellulose adversely affect like aprotic dipolar solvents, for example, dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.

In a particular embodiment contains the reaction mixture is less than 5% by weight, preferably less than 2% by weight, in particular less than 0.1% by weight, of further solvents, based on the total weight of the reaction mixture.

Farther Is it possible to stop the degradation reaction when the desired degree of degradation is reached is by adding appropriate amounts of acylating agent, which react with remaining water.

The so obtained solution will now be used in step B).

To the solution obtained from step A) Now the acylating agent is given.

The Carboxylic acid derivative of the formula IV or the ketene of the formula V can in substance, in a ionic liquid or in a suitable solvent solved be added. As a solvent For example, ethers such as diethyl ether, methyl tert-butyl ether, Terahydrofuran or dioxane, or ketones, such as dimethylketone, or halogenated hydrocarbons, such as dichloromethane, trichloromethane or dichloroethane. The amount of solvent used becomes the carboxylic acid derivative of formula IV or the ketene of formula V should be measured that no precipitation the cellulose enters during the addition. As an ionic liquid Preferably, the one in which the cellulose itself - as above described - is solved.

If the carboxylic acid derivative of the formula IV or the ketene of the formula V is gaseous, it may be in the solution be gelled by cellulose in the ionic liquid.

In a particular embodiment becomes the carboxylic acid derivative of the formula IV or the ketene of the formula V in substance.

In another particular embodiment becomes the carboxylic acid derivative of the formula IV or the ketene of the formula V in an ionic liquid solved added, with particular preference the ionic liquid which is also used to solve the cellulose is used.

There is also the possibility that one or more further solvents are added to the reaction mixture or are already supplied with the solution obtained from step A) or the carboxylic acid derivative of the formula IV or the ketene of the formula V. Suitable solvents in this case are those solvents which do not adversely affect the solubility of the cellulose, such as aprotic dipolar solvents, for example dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane. Wei terhin, nitrogen-containing bases, such as pyridine, etc., can also be added.

In a particular embodiment contains the reaction mixture in addition to the ionic liquid and possibly the solvent, in which the carboxylic acid derivative of the formula IV or the ketene of the formula V is dissolved, less than 5 wt.%, preferably less than 2% by weight, in particular less than 0.1% by weight, based on the total weight of the reaction mixture, on further solvents and / or additional nitrogenous bases.

In the event that carboxylic acid derivatives of the formula IV with X =Hal or OCOR.sup.x ^' are used as the acylating agent, it may also be expedient to carry out the acylation in the presence of a tertiary amine, for example triethylamine, of an aromatic nitrogen base, for example pyridine, or mixtures thereof to perform. The teriary amine, the aromatic nitrogen base or the mixtures thereof are usually used in a stoichiometric ratio. On a case-by-case basis, an excess or a deficit can also be beneficial.

In the event that ketenes of the formula V are used as the acylating agent, it is also possible to carry out the acylation according to the invention in the presence of a catalyst. Suitable for this purpose are the alkali metal or alkaline earth metal salts of C ₁ -C ₄ -alkanecarboxylic acids or benzoic acid. Examples of these are sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium benzoate or potassium benzoate, preferably sodium acetate. However, it is also possible to use the acids themselves, that is to say the C ₁ -C ₄ -alkanecarboxylic acids or benzoic acid. The catalyst is usually used in amounts of up to 10 mol%, preferably up to 8 mol%, based on the ketene of the formula V.

The Implementation becomes dependent from the ionic liquid used and the carboxylic acid derivative used of the formula IV or of the ketene of the formula V used at a temperature of melting point of the ionic liquid up to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C carried out.

In the case of carboxylic acid derivatives of the formula IV or ketene of the formula V which are liquid or solid at the reaction temperature, the reaction is usually carried out at ambient pressure. However, it may also be advantageous on a case-by-case basis to work at overpressure, in particular when a volatile carboxylic acid derivative of the formula IV or ketene of the formula V is used. As a rule, the reaction is carried out in air. But it is also possible under inert gas, so for example under N ₂ , a noble gas or mixtures thereof, to work.

at Carboxylic acid derivatives of the formula IV or ketenes of the formula V, which are gaseous at the reaction temperature, it may be beneficial to the reaction under the autogenous pressure of Reaction mixture at the desired Reaction temperature to perform or at a pressure higher is, as the autogenous pressure of the reaction system.

It but may also be advantageous, the reaction with a carboxylic acid derivative of the formula IV or a ketene of the formula V, which at the reaction temperature gaseous is to carry out under ambient pressure and the gaseous carboxylic acid derivative of formula IV or the ketene of formula V in excess to use.

In dependence from the desired The degree of substitution of the cellulose is the amount of acylating agent used - in each case in relation to to the cellulose used - the Reaction time and optionally set the reaction temperature.

For example, if it is desired to fully acylate the cellulose, which is composed on average of u anhydroglucose units, 3u equivalents of acylating agent are needed. Preferably, in this case the stoichiometric amount of acylating agent (n _acylating / n _{anhydroglucose units} = 3) or an excess is used, preferably an excess of up to 1000 mol% based on u. If it is desired to partially acylate the cellulose, which is composed on average of u anhydroglucose units, the amount of acylating agent used is usually adjusted (n _{acylating agent} (s) _{anhydroglucose units} <3). The smaller the quotient n _{acylating agent} (s) _{anhydroglucose units} , the lower will be the average degree of substitution of the acylated cellulose under otherwise identical conditions and the same reaction time.

Furthermore, it is possible to terminate the acylation reaction when the desired degree of acylation tion is achieved by the acylated cellulose is separated from the reaction mixture. This can be achieved, for example, by adding an excess of water or other suitable solvent in which the acylated cellulose is not soluble, but the ionic liquid is readily soluble, such as a lower alcohol such as methanol, ethanol, propanol or butanol, or with a ketone For example, diethyl ketone, etc., or mixtures thereof, take place. The choice of suitable solvent is also determined by the particular degree of substitution and the substituents of the cellulose. Preferably, an excess of water or methanol is used.

The Work-up of the reaction mixture is usually carried out by the acylated Cellulose is precipitated as described above and the acylated Cellulose is filtered off. But it is also possible separation by centrifugation perform. From the filtrate or the centrifugate can by conventional methods, the ionic liquid be recovered by the volatile components, such. the precipitant, or excess acylating agent (or reaction products and / or hydrolysis products of the acylating agent) etc. are distilled off. The remaining ionic liquid can again in the inventive method be used.

It but it is also possible the reaction mixture in water or in another suitable solvent, in which the acylated cellulose is insoluble, the ionic liquid but easily soluble is such as a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example diethyl ketone etc. or mixtures thereof, and depending on the embodiment For example, to obtain fibers, films of acylated cellulose. The choice of the appropriate Lösusungsmittels is also determined by the respective degree of substitution and the substituents determined the cellulose. The filtrate is as described above worked up.

Farther Is it possible abort the acylation reaction when the desired degree acylation is achieved by cooling the reaction mixture and worked up. The work-up can be described after the above Methods are done.

Of the Termination of the acylation reaction can also be done so that to a given time still existing acylating agent from the reaction mixture by distillation, stripping or extraction with a solvent, that with the ionic liquid forms two phases, is removed.

In another embodiment of the present invention two or more acylating agents used. This can be a Mixture of two (or more) carboxylic acid derivatives of formula IV or ketenes of the formula V in analogy to the above procedure be used. But it is also possible first with the first Acylating the reaction to a DS = a (<3) to perform and then with a second acylating agent, the reaction to a DS = b, where a <b ≦ 3.

at In this embodiment, acylated celluloses are obtained. which two (or more) different acyl groups (depending on of the acylating agents used).

In the case, that the ionic liquid guided in circulation mode becomes, in one embodiment, the ionic liquid purified, for example, from the precipitant, possibly added other solvents, Hydrolysis and degradation products of the acylating agent, etc., and again in step A). In a further embodiment can the ionic liquid, which up to 15 wt .-%, preferably up to 10 wt .-%, in particular up to 5% by weight of precipitant (s) etc. as described above, used in step A) become. However, this may be necessary on a case-by-case basis for example, if the precipitant carries free hydroxy groups, the solution obtained in step A), before it is used in step B), of any remaining precipitant etc., for example, by the remaining precipitant etc. is distilled off, or a corresponding excess of acylating agent is used.

The Method may be discontinuous, semi-continuous or continuous, carried out become.

• • der Gruppe der halogenhaltigen Verbindungen und der Pseudohalogenide der Formel: BF₄ ^–, PF₆ ^–, CF₃SO₃ ^–, (CF₃SO₃)₂N^–, CF₃CO₂ ^–, CCl₃CO₂ ^–, CN^–, SCN^–, OCN^–
• • der Gruppe der Sulfate, Sulfite und Sulfonate der allgemeinen Formel: SO₄ ^2–, HSO₄ ^–, SO₃ ^2–, HSO₃ ^–, R^aOSO₃ ^–, R^aSO₃ ^–
• • der Gruppe der Phosphate der allgemeinen Formel PO₄ ^3–, HPO₄ ^2–, H₂PO₄ ^–, R^aPO₄ ^2–, HR^aPO₄ ^–, R^aR^bPO₄ ^–
• • der Gruppe der Phosphonate und Phosphinate der allgemeinen Formel: R^aHPO₃ ^–, R^aR^bPO₂ ^–, R^aR^bPO₃ ^–
• • der Gruppe der Phosphite der allgemeinen Formel: PO₃ ^3–, HPO₃ ^2–, H₂PO₃ ^–, R^aPO₃ ^2–, R^aHPO₃ ^–, R^aR^bPO₃ ^–
• • der Gruppe der Phosphonite und Phosphinite der allgemeinen Formel: R^aR^bPO₂ ^–, R^aHPO₂ ^–, R^aR^bPO^–, R^aHPO^–
• • der Gruppe der Carbonsäuren der allgemeinen Formel: R^aCOO^–
• • der Gruppe der Borste der allgemeinen Formel: BO₃ ^3–, HBO₃ ^2–, H₂BO₃ ^–, R^aR^bBO₃ ^–, R^aHBO₃ ^–, R^aBO₃ ^2–, B(OR^a)(OR^b)(OR^c)(OR^d)^–, B(HSO₄)^–, B(R^aSO₄)^–
• • der Gruppe der Boronate der allgemeinen Formel: R^aBO₂ ^2–, R^aR^bBO^–
• • der Gruppe der Silikate und Kieselsäuresäureester der allgemeinen Formel: SiO₄ ^4–, HSiO₄ ^3–, H₂SiO₄ ^2–, H₃SiO₄ ^–, R^aSiO₄ ^3–, R^aR^bSiO₄ ^2–, R^aR^bR^cSiO₄ ^–, HR^aSiO₄ ^2–, H₂R^aSiO₄ ^–, HR^aR^bSiO₄ ^–
• • der Gruppe der Alkyl- bzw. Arylsilan-Salze der allgemeinen Formel: R^aSiO₃ ^3–, R^aR^bSiO₂ ^2–, R^aR^bR^cSiO^–, R^aR^bR^cSiO₃ ^–, R^aR^bR^cSiO₂ ^–, R^aR^bSiO₃ ^2–
• • der Gruppe der Carbonsäureimide, Bis(sulfonyl)imide und Sulfonylimide der allgemeinen Formel:
  
• • der Gruppe der Methide der allgemeinen Formel:
  

The present invention also provides a process for the acylation of cellulose with carboxylic acid derivatives of the formula IV, as defined above, in an ionic liquid of the formula I ([A] + / n, [Y] ^n- ), or of the formulas IIa, b , or c ([A ¹ ] ⁺ [A ² ] ⁺ [Y] ^n- , ^where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ^n- ), ^where n = 3; or [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ^n- , where n = 4), where [A] _n ⁺ , [A ¹ ] ⁺ , [[A ² ] ⁺ , [[ A ³ ] ⁺ , [A ³ ] ⁺ , [A ⁴ ] ^{+ are} as defined above and [wherein [Y] ^{n -} may be selected from

• The group of halogen-containing compounds and pseudohalides of the formula: BF ₄ ^- , PF ₆ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₃ ) ₂ N ^- , CF ₃ CO ₂ ^- , CCl ₃ CO ₂ ^- , CN ^- , SCN ^- , OCN ^-
• • the group of sulfates, sulfites and sulfonates of the general formula: SO ₄ ^2- , HSO ₄ ^- , SO ₃ ^2- , HSO ₃ ^- , R ^a OSO ₃ ^- , R ^a SO ₃ ^-
• • the group of phosphates of the general formula PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^-
• The group of phosphonates and phosphinates of the general formula: R ^a HPO ₃ ^- , R ^a R ^b PO ₂ ^- , R ^a R ^b PO ₃ ^-
• The group of phosphites of the general formula: PO ₃ ^3- , HPO ₃ ^2- , H ₂ PO ₃ ^- , R ^a PO ₃ ^2- , R ^a HPO ₃ ^- , R ^a R ^b PO ₃ ^-
• The group of phosphonites and phosphinites of the general formula: R ^a R ^b PO ₂ ^- , R ^a HPO ₂ ^- , R ^a R ^b PO ^- , R ^a HPO ^-
• • the group of carboxylic acids of the general formula: R ^a COO ^-
• • the group of bristles of the general formula: BO ₃ ^3- , HBO ₃ ^2- , H ₂ BO ₃ ^- , R ^a R ^b BO ₃ ^- , R ^a HBO ₃ ^- , R ^a BO ₃ ^2- , B (OR ^a ) (OR ^b ) (OR ^c ) (OR ^d ) ^- , B (HSO ₄ ) ^- , B (R ^a SO ₄ ) ^-
• The group of boronates of the general formula: R ^a BO ₂ ^2- , R ^a R ^b BO ^-
• 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 ^a SiO ₄ ^3- , R ^a R ^b SiO ₄ ^2- , R ^a R ^b R ^c SiO ₄ ^- , HR ^a SiO ₄ ^2- , H ₂ R ^a SiO ₄ ^- , HR ^a R ^b SiO ₄ ^-
• • the group of alkylsilane and arylsilane salts of the general formula: R ^a SiO ₃ ^3-, R ^a R ^b SiO ₂ ^2-, R ^a R ^b R ^c SiO ^-, R ^a R ^b R ^c SiO ₃ ^-, R ^a R ^b R ^c SiO ₂ ^- , R ^a R ^b SiO ₃ ^2-
• The group of the carboxylic imides, bis (sulfonyl) imides and sulfonyl imides of the general formula:
  
• The group of methides of the general formula:
  

The Meaning of the variable is as defined above. Likewise apply Here, the embodiments and procedures described above analogous.

The The following examples serve to illustrate the invention.

Preamble:

Avicel PH 101 and Linters were over Night at 80 ° C or 105 ° C and dried in each case 0.05 mbar.

The ionic liquids were over Night at 120 ° C and 0.05 mbar with stirring dried.

Abbreviations:

• BMIM Cl

  1-butyl-3-methylimidazolium chloride

  BMIM Ac

  1-butyl-3-methylimidazolium ChloridDS average degree of substitution

Example 1:

In a 25 ml flask with magnetic stirrer and reflux condenser, 0.5 g of Linters (DP 3250) were introduced into 9.5 g of BMIM Cl at 120 ° C. and stirred under nitrogen for 2 hours until a clear solution had formed. After addition of 5.90 mg of p-toluene sulfonic acid monohydrate was stirred at 100 ° C for 6 hours. To that Mixture was then added 3.0 g of acetic anhydride and stirred at 100 ° C for a further 16 hours. After cooling to room temperature, the mixture was added to 200 ml of methanol, the precipitated reaction product was filtered off, washed three times with 20 ml of methanol and dried at 60 ° C and 0.05 mbar for 16 hours to constant weight.

This gave 0.85 g (90% of theory) of a white product having an average degree of substitution of 2.9 ( ¹ H-NMR spectroscopically determined) and an average degree of polymerization of 180.

Example 2:

In a 100 ml flask with magnetic stirrer and reflux condenser under argon at 100 ° C 1.072 g Avicel PH 101 in 11 ml BMIM Ac and 2 hours touched, until a clear solution originated. After addition of 4.0 g of acetic anhydride was 16 hours at 100 ° C touched. After cooling at room temperature, the mixture was added to 200 ml of methanol, the precipitated reaction product is filtered off with suction, three times with 20 ml of methanol washed and at 60 ° C and 0.05 mbar for 16 hours to constant weight dried.

This gave 1.708 g (91% of theory) of a beige solid having an average degree of substitution of 2.9 ( ¹ H NMR determined spectroscopically).

Claims (21)

Process for the acylation of poly- or oligosaccharides, characterized in that one dissolves a poly- or oligosaccharide, in at least one ionic liquid and in step A) with at least one acid, optionally with the addition of water (step A1), or optionally with the addition of water, at elevated temperature (step A2), and in step B), the poly- or oligosaccharide thus obtained, whose DP is lower than that of the poly- or oligosaccharide used, reacted with an acylating agent. Method according to claim 1, characterized in that in that a polysaccharide is used as the polysaccharide or olosaccharide. Method according to claim 2, characterized in that that is used as a polysaccharide cellulose. Process according to claims 1 to 3, characterized in that the ionic liquid, or mixtures thereof, are chosen from the compounds of the formulas I, [A] + / n [Y] (I) where n is 1, 2, 3 or 4; [A] ⁺ for a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation; and [Y] ^n- for a mono-, di-, tri- or tetravalent anion; stand; or the compounds of the formula II [A ¹ ] ⁺ [A ² ] ⁺ [Y] ^n- (IIa) where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ^n- (IIb) where n = 3; or [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ^{n -} (IIc) where n = 4 and where [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ ; and [Y] ^{n- have} the abovementioned meaning. A method according to claim 4, characterized in that [A] ⁺ for a cation selected from the compounds of formulas (IIIa) to (IIIy)

and oligomers containing this structure, wherein • the radical R is hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Radical with 1 to 20 carbon atoms; and • the radicals R ¹ to R ⁹ independently of one another are hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups substituted radicals having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) are bonded to a carbon atom (and not to a heteroatom), additionally may also stand for halogen or a functional group; or two adjacent radicals from the series R ¹ to R ⁹ together also represent a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups with 1 to 30 carbon atoms, can stand. Process according to claims 4 or 5, characterized in that [Y] ^n- is an anion selected from • the group of halides F ^-, Cl ^-, Br ^-, I ^- • group of halogen-containing compounds of the formula: F ^-, Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₃ ) ₂ N ^- , CF ₃ CO ₂ ^- , CCl ₃ CO ₂ ^- , CN ^- , SCN ^- , OCN ^- • the group of sulfates, sulfites and sulfonates of the general formula: SO ₄ ^2- , HSO ₄ ^- , SO ₃ ^2- , HSO ₃ ^- , R ^a OSO ₃ ^- , R ^a SO ₃ ^- • the group of phosphates of the general formula PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^- • the group of phosphonates and phosphinates of the general formula: R ^a HPO ₃ ^- , R ^a R ^b PO ₂ ^- , R ^a R ^b PO ₃ ^- • the group of phosphites of the general formula: PO ₃ ^3- , HPO ₃ ^2- , H ₂ PO ₃ ^- , R ^a PO ₃ ^2- , R ^a HPO ₃ -, R ^a R ^b PO ₃ ^- • the group of phosphonites and phosphinites of the general Formula: R ^a R ^b PO ₂ ^- , R ^a HPO ₂ ^- , R ^a R ^b PO ^- , R ^a HPO ^- • the group of carboxylic acids of the general formula: R ^a COO ^- • the group of the bristles of the general formula: BO 3 ^3- , HBO ₃ ^2- , H ₂ BO ₃ ^- , R ^a R ^b BO ₃ ^- , R ^a HBO ₃ ^- , R ^a BO ₃ ^2- , B (OR ^a ) (OR ^b ) (OR ^c ) (OR ^d ) ^- , B (HSO ₄ ) ^- , B (R ^a SO ₄ ) ^- • the group of boronates of the general formula: R ^a BO ₂ ^2- , R ^a R ^b BO ^- • 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 ^a SiO ₄ ^3- , R ^a R ^b SiO ₄ ^2- , R ^a R ^b R ^c SiO ₄ ^- , HR ^a- SiO ₄ ^2- , H ₂ R ^a SiO ₄ ^- , HR ^a R ^b SiO ₄ ^- • the group of the alkyl or aryl silane salts of the general formula: R ^a SiO ₃ ^3- , R ^a R ^b SiO ₂ ^2-, R ^a R ^b R ^c SiO ^-, R ^a R ^b R ^c SiO ₃ ^-, R ^a R ^b R ^c SiO ₂ ^-, R ^a R ^b SiO ₃ ^2- • the group of carboximides, sulfonyl bis ( ) imides and sulfonylimides of the general formula:

The group of methides of the general formula:

wherein the radicals R ^a , R ^b , R ^c and R ^d are each independently hydrogen, C ₁ -C ₃₀ -alkyl, optionally by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C ₂ -C ₁₈ alkyl, C ₆ -C ₁₄ aryl, C ₅ -C ₁₂ cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, wherein two of them together form an unsaturated , saturated or aromatic, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups interrupted ring, said radicals each additionally by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen , Heteroatoms and / or heterocycles may be substituted; stands. Process according to claims 4 to 6, characterized in that [A] ⁺ for a cation selected from the group of the compounds IIIa, IIIe, IIIf; IIIg, IIIg ', IIIh, IIIi, IIIj, IIIj', IIIk, IIIk ', IIIl, IIIm, IIIm', IIIn or IIIn '. Process according to claims 4 to 7, characterized in that [A] ^{+ represents} a cation selected from the group of the compounds IIIa, IIIe or IIIf. Process according to claims 4 to 8, characterized in that [Y] ^{n- is} selected for an anion from the group of halides, group of halogen-containing compounds, the group of carboxylic acids, the group containing SO ₄ ^2- , SO ₃ ^2- , R ^a OSO ₃ ^- and R ^a SO ₃ ^- , and the group containing PO ₄ ^3- and R ^a R ^b PO ₄ ^- , stands. Process according to claims 1 to 9, characterized that step A1) is carried out as step A). Method according to claim 10, characterized in that that as acid an inorganic acid, an organic acid or mixtures thereof. Process according to claims 1 to 9, characterized that step A2) is carried out as step A). Process according to claims 1 to 12, characterized in that in step B) as the acylating agent, a carboxylic acid derivative of formula IV

where the radicals have the following meanings: R ^x , R ^{x '} H, C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, C ₂ -C ₃₀ -alkynyl, C ₃ -C ₁₂ -cycloalkyl, C ₅ - C ₁₂ -cycloalkenyl, aryl or heterocyclyl, where these seven latter radicals may optionally be substituted; X is halogen, imidazol-1-yl or O-COR ^{x '} ; or a ketene of formula Va or a diketene of formula Vb1 or a mixed diketene of formula Vb2

where the radicals have the following meaning: R ^y , R ^{y '} , R ^z , R ^{z' is} hydrogen, C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, C ₂ -C ₃₀ -alkynyl C ₃ -C ₁₂ -Cycloalkyl, C ₅ -C ₁₂ cycloalkenyl, aryl or heterocyclyl, where the latter seven radicals may be optionally substituted; or R ^y and R ^z or R ^{y '} and R ^z' together form an optionally substituted -Y _o - (CH ₂ ) _p -, - (CH ₂ ) _q -Y- (CH ₂ ) _r - or a - CH = CH-CH = CH- chain, wherein YO, S, S (= O), S (= O) ₂ , NH or NC ₁ -C ₆ alkyl; o is 0 or 1; p is 2, 3, 4, 5, 6, 7 or 8; q, r is 1, 2, 3, 4, 5 or 6; mean; starts. Method according to claim 13, characterized in that in that the acylating agent used is a carboxylic acid derivative of the formula IV. Method according to claim 14, characterized in that in that the acylating agent used is a carboxylic acid derivative of the formula IV X = halogen, preferably chloride. A method according to claim 14, characterized in that the acylating agent is a carboxylic acid derivative of the formula IV with X = OCOR ^{x '} , preferably with OCOR ^x . Method according to claim 13, characterized in that in that a ketene of the formula V is used as the acylating agent. Process according to claims 1 to 17, characterized in that the initial concentration of poly- or oligosaccharide, in ionic liquid in a range of 0.1 to 50 wt .-% based on the Total weight of the solution is. Process according to claims 1 to 18, characterized that steps A and B are at a temperature of melting point the ionic liquid up to 200 ° C carried out becomes. Process according to claims 1 to 19, characterized that the acylated obtained in the acylation in step B) Poly- or oligosaccharide by adding a solvent, in which the acylated polysaccharide is not soluble quenches. Process for the acylation of poly- or oligosaccharides, characterized in that the poly- or oligosaccharide in at least one ionic liquid of formula I, IIa, IIb or IIc, wherein [A] _n ⁺ , [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ have} the meaning given in claim 4 and [Y] ^{n -} for an anion selected from the group of the halides: F-, Cl-, Br-, I- • Group of halogen-containing compounds of the formula: F-, Cl-, Br-, I-, BF ₄ -, PF ₆ -, CF ₃ SO ₃ -, (CF ₃ SO ₃ ) ₂ N-, CF ₃ CO ₂ -, CCl ₃ CO ₂ , CN, SCN, OCN • of the group of sulfates, sulfites and sulfonates of the general formula: SO ₄ ^2- , HSO ₄ ^- , SO 3 ^2- , HSO ₃ ^- , R ^a OSO ₃ ^- , R ^a SO ₃ ^- • the group of phosphates of the general formula PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^- • the group the phosphonates and phosphinates of the general formula: R ^a HPO ₃ -, R ^a R ^b PO ₂ -, R ^a R ^b PO ₃ - • the group of phosphites of the general my formula: PO ₃ ^3- , HPO ₃ ^2- , H ₂ PO ₃ ^- , R ^a PO ₃ ^2- , R ^a HPO ₃ ^- , R ^a R ^b PO ₃ ^- • the group of phosphonites and phosphinites of the general formula: R ^a R ^b PO ₂ ^- , R ^a HPO ₂ ^- , R ^a R ^b PO ^- , R ^a HPO ^- • the group of the carboxylic acids of the general formula: R ^a COO ^- • the group of the bristles of the general formula: BO ₃ ^{3 -} , HBO ₃ ^2- , H ₂ BO ₃ ^- , R ^a R ^b BO ₃ ^- , R ^a HBO ₃ ^- , R ^a BO ₃ ^2- , B (OR ^a ) (OR ^b ) (OR ^c ) (OR ^d ) ^- , B (HSO ₄ ) ^- , B (R ^a SO ₄ ) ^- • the group of boronates of the general formula: R ^a BO ₂ ^2- , R ^a R ^b BO ^- • 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 ^a SiO ₄ ^3- , R ^a R ^b SiO ₄ ^2- , R ^a R ^b R ^c SiO ₄ ^- , HR ^a- SiO ₄ ^2- , H ₂ R ^a SiO ₄ ^- , HR ^a R ^b SiO ₄ ^- • the group of the alkyl or aryl silane salts of the general formula: R ^a SiO ^{3 3-} , R ^a R ^b SiO ^{2 2-} , R ^a R ^b R ^c SiO ^- , R ^a R ^b R ^c SiO ₃ ^- , R ^a R ^b R ^c SiO ₂ ^- , R ^a R ^b SiO ₃ ^2- • the group of carboximides, bis (sulfonyl) imides and sulfonylimides of the general formula:

The group of methides of the general formula:

wherein the radicals R ^a , R ^b , R ^c and R ^d are each independently hydrogen, C ₁ -C ₃₀ -alkyl, optionally substituted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C ₂ -C ₁₈ alkyl, C ₆ -C ₁₄ aryl, C ₅ -C ₁₂ cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, two of them together may form an unsaturated, saturated or aromatic, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups ring, wherein said radicals in each case to additionally may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles; stands; with a carboxylic acid derivative of the formula IV as described in claim 13.