EP2038307A1

EP2038307A1 - Method for acylating cellulose with a specific average degree of polymerization

Info

Publication number: EP2038307A1
Application number: EP07730255A
Authority: EP
Inventors: Klemens Massonne; Veit Stegmann; Giovanni D'andola; Werner Mormann; Markus Wezstein; Wei Leng
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-06-30
Filing date: 2007-06-20
Publication date: 2009-03-25
Also published as: WO2008000666A1; US20090182138A1

Abstract

The present invention describes a method for acylating polysaccharides or oligosaccharides in which a polysaccharide or oligosaccharide is dissolved in at least one ionic liquid and, in step A), is treated with at least one acid, optionally with the addition of water (step A1), or optionally with the addition of water at an elevated temperature (step A2), and the polysaccharides or oligosaccharides so obtained, the DP of which is lower than that of the polysaccharides or oligosaccharides used, is reacted in step B) with an acylating agent.

Description

Process for the acylation of cellulose with a targeted average degree of polymerization

The present invention describes a process for the acylation of cellulose with a targeted average degree of polymerization (DP) by subjecting cellulose in a first step to targeted degradation and in a second step to acylation.

Cellulose is the most important renewable raw material and represents an important starting material for, for example, the textile, paper and nonwoven industries. It also serves as a raw material for derivatives and modifications of cellulose, to which cellulose ethers, e.g. Methylcellulose and carboxymethylcellulose, cellulose esters based on organic acids, e.g. Cellulose acetate, cellulose butyrate, and cellulose esters based on inorganic acids, e.g. Cellulose nitrate, and others count. These derivatives and modifications find a variety of applications, for example in the textile, food, construction and paint industries. Of particular interest here is cellulose acetate.

In the industrial production of cellulose acetate, cotton linters or processed wood pulp are reacted with acetic anhydride in the presence of sulfuric acid or perchloric acid as a catalyst. In this procedure, both a decrease of the DP and an acylation of the hydroxy functions of the anhydroglucan units of the cellulose occur. The decrease in the chain length of the cellulose main body is attributed to a hydrolytic cleavage of the glycosidic bonds, as a consequence of the strongly acidic reaction conditions. Furthermore, the cellulose acetate thus obtained has a degree of substitution (DS) of 3 (= cellulose triacetate). For the spinning, however, a DS of about 2.5 is necessary. Therefore, cellulose triacetate is subjected to partial deacylation. The disadvantage here is that initially a heterogeneous mixture is present in this process, which passes over in the course of the reaction into a more or less homogeneous mixture. The handling of such mixtures has very high technical requirements. It is also disadvantageous that primarily a cellulose acetate having a DS of 3 is obtained. Furthermore, the DP of the resulting cellulose acetate strongly depends on the quality of the cellulose used and the reaction conditions.

Thus, there is a need to provide a simple method for targeted presentation of acylated celluloses with a targeted DP and a defined DS.

A process has now been found for the preparation of acylated celluloses with a targeted DP and a defined DS by dissolving cellulose in an ionic liquid, and the resulting solution in a first step (step A). treated with an acid (optionally with the addition of water) or at elevated temperature (optionally in the presence of water) and in a second step (step B) the resulting cellulose whose DP is lower than that used in step A. Cellulose, reacted with an acylating agent. 5

Ionic liquids in the sense of the present invention are preferred

(A) Salts of the general formula (I)

i o [A]; [YΓ (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 "is a one, two or more -, tri- or tetravalent anion stands 15

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

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

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ⁿ - (IIb), where n = 3; or 20 [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ⁿ - (Mc), where n = 4 and

where [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are selected} independently of one another from the groups mentioned for [A] ⁺ and [Y] ^π "the meaning mentioned under (A) owns 25

Preferably, the ionic liquids have a melting point of less than 180 ° C. More preferably, the melting point is in a range of -50 ° C to 150 ° C, more preferably in the range of -20 ° C to 120 ° C, and most preferably below 100 ° C. 30

The ionic liquids of the invention are organic compounds, i. in that at least one cation or anion of the ionic liquid contains an organic radical.

Compounds which are suitable for forming the cation [A] ⁺ of ionic liquids are known, for example, from DE 102 02 838 A1. Thus, such compounds may contain oxygen, phosphorus, sulfur or in particular nitrogen atoms, for example at least one nitrogen atom, preferably 1 to 10 nitrogen atoms, more preferably 1 to 5, most preferably 1 to 3 and especially 1 to

40 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, of which then, in equilibrium, a proton or an alkyl group can be transferred to the anion to form an electrically neutral molecule.

In the case where the nitrogen atom is the carrier of the positive charge in the cation of the ionic liquid, in the synthesis of the ionic liquids a cation can first be generated by quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle. The quaternization can be carried out by alkylation of the nitrogen atom. Depending on the alkylating reagent used, salts with different anions are obtained. In cases where it is not possible to form the desired anion already during quaternization, this can be done in a further synthesis step. Starting from, for example, an ammonium halide, the halide can be reacted with a Lewis acid to form a complex anion from halide and Lewis acid. Alternatively, replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt with precipitation of the metal halide formed, via an ion exchanger or by displacement of the halide ion by a strong acid (with liberation of the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 12, 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 6 -alkyl, preferably C 1 -C 10 -alkyl, particularly preferably C 1 -C 6 -alkyl and very particularly preferably methyl. The alkyl group may be unsubstituted or have one or more identical or different substituents.

Preference is given to those compounds which contain at least one five- to six-membered heterocycle, in particular a five-membered heterocycle, which has at least one nitrogen atom and, if appropriate, an oxygen or sulfur atom. Also particularly preferred are those compounds containing at least one 5- to 6-membered heterocycle having one, two or three nitrogen atoms and one sulfur or one oxygen atom, most preferably those having two nitrogen atoms. Further preferred are aromatic heterocycles.

Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol and in particular below 350 g / mol.

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

(MId) (MIe) (MIf)

Ciig> (MIh)

(INJ) (MIj ') (MIk) (MIk ')

(Ulm) (MIm ') (MIn)

(MIp) (MIq) (MIq ')

(HIq ") (Me) (MIr ')

(MIr ") (MIs) (With)

(MIu) (MIv) (MIw)

and oligomers containing these structures.

Further suitable cations are compounds of the general formula (MIx) and (MIy)

R ² R ²

₃ 1 -H ₁ I + ₁

R-P-R S-R

I i

R R

(MIx) (MIy)

and oligomers containing these structures.

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

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

• the radicals R ¹ to R ⁹ independently represent hydrogen, a sulfo

Group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or aromatic aliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms, where the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) to a carbon atom (and not to a heteroatom) may additionally be also halogen or a functional group; or

two adjacent radicals from the series R ¹ to R ⁹ together also for a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or by 1 to 5 heteroatoms or functional

Groups interrupted or substituted radical having 1 to 30 carbon atoms.

Suitable hetero atoms in the definition of the radicals R and R ¹ to R ^{9 are in} principle all heteroatoms in question which are capable of formally a -CH ₂ -, a -CH =, a -C≡ or a = C = group to replace. When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. Particular preferred groups are -O-, -S-, -SO-, -SO2-, -NR'-, -N =, - PR'-, -PR'3 and -SiRV, where the radicals R 'is the remainder of the carbon-containing residue. The radicals R ¹ to R ⁹ may in the cases in which they are bonded in the abovementioned formulas (III) to a carbon atom (and not to a heteroatom) also be bonded directly via the heteroatom.

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

Halogens are fluorine, chlorine, bromine and iodine.

The radical R preferably stands for

• unbranched or branched, unsubstituted or one to several times with

Hydroxyl, halogen, phenyl, cyano, C 1 -C 6 -alkoxycarbonyl and / or SO 3 H-substituted C 1 -C 20 -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 , Trifluoromethyl,

Difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopro- pyl, 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 Ci-Cβ-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 θ) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^{B is} preferably hydrogen, methyl or ethyl and m is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6 Dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;

• vinyl;

1-propen-1-yl, 1-propen-2-yl and 1-propen-3-yl; and

• N, N-di-Ci-Cδ-alkyl-amino, such as N, N-dimethylamino and N ₁ N-diethylamino.

The radical R particularly preferably represents unbranched and unsubstituted C 1 -C 8 -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 also CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH2 and _CH3 CH2θ- (CH2CH2θ) _m -CH ₂ CH 2 with m = 0 to. 3

The radicals R ¹ to R ⁹ are preferably each independently

• hydrogen;

• halogen;

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

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

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cycloalkyl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cycloalkenyl; or

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

two adjacent radicals together for

An unsaturated, saturated or aromatic, if appropriate by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or

Heterocycles substituted and optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups ring.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles Ci-cis-alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2- Butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl 1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl , 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3 -Methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1 butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, 1- Nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, Cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, α, α-dimethylbenzyl, p-tolylmethyl, 1- (p Butyl-phenyl) -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, A-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropy 1, A-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6- Dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, acetyl, C _m F 2 ( _m -a) + (ib) H 2a + b with m equal to 1 to 30, 0 < a <m and b = 0 or 1 (for example CF3, C2F5, CH2CH2-C ( _m -2) F2 (m-2) + i, C ₆ Fi ₃ , C ₈ Fi ₇ , C10F21, Ci ₂ 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- (methoxy - carbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, butylthio - methyl, 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-oxa-heptyl, 1-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5, 10-dioxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 1 1-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa -heptyl, 1-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa- tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 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-oxato-tetradecyl.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C2-Cis Alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F2 (ma) - (ib) H2a-b with im <30, 0 <a < m and b = 0 or 1. When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C6-Ci2-aryl is preferably phenyl, ToIyI, XyIyI, α-naphthyl, ß-naphthyl, 4-diphenylyl, Chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl , Ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2.6 Dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C6F (5- _a ) H _a with 0 <a <5.

C 5 -C 12 -cycloalkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, Diethylcyclohe- xyl, butylcyclohexyl, methoxycyclohexyl, Dimethoxycyclohexyl, Diethoxycyclohexyl, Butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F2 _(m -a) - (ib) H2a-b in the <30, 0 <a <m and b = 0 or 1 and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C5-Ci2-cycloalkenyl is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclo hexadienyl or C _n F2 _(m -a) -3 (ib) H2a-3b in the <30, 0 <a <m and b = 0 or the first

An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle 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-Ci-C4-alkyl 1-aza-1, 3-propenylene, 1,4-butan-1, 3-dienylene, 1-az-1, 4-buta-1,3-dienylene or 2-aza-1,4-buta-1, 3-dienylene. If the abovementioned radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the remainder, preferably not more than 4 and very particularly preferably not more than 3.

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

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

• hydrogen;

• straight-chain or branched, unsubstituted or monosubstituted to polysubstituted by hydroxyl, halogen, phenyl, cyano, Ci-Cδ-alkoxycarbonyl and / or SO3H Ci-Cis-alkyl having a total of 1 to 20 carbon atoms, such as methyl, ethyl, 1-propyl , 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3 -methyl-1-butyl,

2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl 1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3 pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl,

1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl ) -ethyl, 2- (n-butoxy-carbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;

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

R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ θ) _m -CH ₂ CH ₂ CH ₂ CH ₂ - 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-trioxa-undecyl, 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 are each independently hydrogen or Ci-Cis-alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, phenyl for 2-hydroxyethyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N-diethylamino , for chlorine as well as for CH3O-

(CH ₂ CH2θ) _m -CH ₂ CH 2 and CH ₃ CH2θ- (CH2CH2θ) _m -CH ₂ CH 2 with m = 0 to. 3

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

• one of the radicals R ¹ to R ^{5 is} methyl, ethyl or chlorine and the remaining radicals R ¹ to R ^{5 are} hydrogen;

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

• all of the radicals R ¹ to R ⁵ are hydrogen;

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

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

and in particular those in which

• R ¹ to R ^{5 are} hydrogen; or

• one of the radicals R ¹ to R ^{5 is} methyl or ethyl and the remaining radicals R ¹ to R ^{5 are} hydrogen.

Particularly preferred pyridinium ions (IIIa) which may be mentioned are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) -pyridinium, 1 (1-Hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-dodecyl) pyridinium, 1- (1-tetradecyl) pyridinium, 1- (1-hexadecyl) pyridinium, 1, 2-dimethylpyridinium,

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

Very particularly preferred pyridazinium ions (MIb) 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 (MIc) are those in which

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

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

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

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

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

• R ¹ to R ^{4 are} methyl; or

• R ¹ to R ^{4 are} methyl hydrogen.

Very particularly preferred as Imidazoliumionen (Never) are those in which R ^{1 is} hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 1-propen-3-yl, 2-hydroxyethyl or 2-cyanoethyl and R ² to R ⁴ independently of one another are hydrogen, methyl or ethyl.

Very particularly preferred imidazolium ions (MIe) which may be mentioned are 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-Butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-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-methyl imidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3- methyl imidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-H exadecyl) -3-octylimidazolium, 1, 2-dimethylimidazolium, 1, 2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1 - ( 1-hexyl) -2,3-dimethyl-imidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3 ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1, 4,5-trimethyl-3 ethyl imidazolium, 1, 4,5-trimethyl-3-butyl imidazolium, 1, 4,5-trimethyl-3-octyl imidazolium and 1- (prop-1 -en-3-yl) -3-methyl imidazolium.

Very particularly preferred pyrazolium ions (MIf), (MIg) or (MIg ') are those in which

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

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

• R ¹ to R ^{4 are} independently hydrogen or methyl.

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

• independently of one another R ¹ to R ^{6 are} hydrogen or methyl. Very particularly preferably used as 2-pyrazolinium (IMj) or (MIj ') such, in which

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

Very particular preference is given as 3-pyrazolinium (MIk) or (IMk ') such, in which

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

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

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

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

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

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

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

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

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

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

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

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

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

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

With very particular preference one uses as imidazolidinium ions (mit) those in which

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

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

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

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

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

Examples of the tertiary amines of which the quaternary ammonium ions of the general formula (IMu) are derived by quaternization with the radicals R mentioned are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl hexylamine, diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2 ethylhexyl) amine, di-isopropylethylamine, di-isopropyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, di-isopropyl-2-ethylhexyl ) -amine, di-n-butylethylamine, di-n-butyl-n-propylamine, di-n-butyl-n-pentylamine, di-n-butylhexylamine, di-n-butyloctylamine, di-n-butyl (2 -ethyl-hexyl) -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-isopropylpiperidine, Nn-butylpiperidine, N-sec-butylpiperidine, N-tert-butylpiperidine, Nn-pentylpiperidine, Nn-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, Nn-pentylmorpholine, N-benzyl-N-ethylaniline, N-benzyl-Nn-propylaniline, N-benzyl-N-iso-propylaniline, N-benzyl-N-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 (MIu) are those which are derived from the following tertiary amines by quaternization with the abovementioned radicals R, such as diisopropylethylamine, diethyl-tert-butylamine, diisobutylbutylamine, di-isopropylamine n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.

Particularly preferred tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers. Another preferred tertiary amine having three identical residues is triallylamine.

Very particularly preferred as guanidinium ions (MIv) are those in which

• R ¹ to R ^{5 are} methyl.

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

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

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

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

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

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

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

• R ¹ to R ^{3 are} independently C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.

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

Particular preference is given to 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-Octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1, 2-dimethylpyridinium, 1- Ethyl 2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) - 2-methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1, 2-diethylpyridinium, 1- (1-butyl ) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) - 2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1, 2-dimethyl-5-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 -D odecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethylpyridinium, 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium , 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1 - (1-hexadecyl) imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1 - (1-octyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1 , 2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3 dimethyl imidazolium and 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1 , 4-Dimethyl-3-octylimidazolium, 1, 4,5-trimethylimidazolium, 1, 3,4,5-tetramethylimidaz olium, 1, 4,5-trimethyl-3-ethyl imidazolium, 1, 4,5-trimethyl-3-butylimidazolium, 1, 4,5-trimethyl-3-octylimidazolium and 1- (prop-1 -en-3-yl) -3-methylimidazolium.

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

The anion [Y] ⁿ - 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 SOs) 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 ³ OSO ₃ -, R ³ SO ₃ -

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

The group of phosphonates and phosphinates of the general formula: R ³ H PO ₃ -, R ³ R ^b PO ₂ -, R ³ R ^b PO ₃ -

The group of phosphites of the general formula: PO ₃ ^{3 "} , HPO ₃ ^2" , H ₂ PO ₃ -, R ³ PO ₃ ^{2 "} , R ³ HPO ₃ -, R ³ R ^b PO ₃ -

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

• the group of carboxylic acids of the general formula: R ³ COO-

The group of borates of the general formula:

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

The group of the boronates of the general formula: R ³ BO ₂ ² -, R ³ 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 ³ SiO ₄ ^{3 "} , R ³ R ^b Si0 ₄ ^2" , R ³ R ^b R ^ SiO ₄ -, HR ³ SiO ₄ ^{2 "} , H ₂ R ³ SiO ₄ ^" , HR ³ R ^b SiO ₄ - The group of the alkyl or aryl silane salts of the general formula:

R ³ SiO ₃ ^{3 "} , R ^a R ^b Si0 ₂ ² -, R ^a R ^b R ^c SiC-, R ^a R ^b R ^c Si0 ₃ -, R ^a R ^b R ^c Si0 ₂ -, R ^a R ^b Si0 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:

SO ₂ -R ³

R ^b -O ₂ S ^' SO, -R ^C

In this formula, R ^a , R ^b , R ^c and R ^d independently of one another are each hydrogen, C ₁ -C 30 -alkyl, if appropriate by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted Te imino groups interrupted C2-Ci8-alkyl, C6-Ci ₄ -aryl, C5-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, wherein two of them together an unsaturated, saturated or aromatic, optionally 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 can be substituted.

In which are optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted Ci-cis-alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadyl, 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, A-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, A-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, A-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 groups interrupted C2-Ci8-alkyl, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6- dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 1-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5 oxa-nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxa-octyl, 1-methoxy-3,6,9-trioxaundecyl, 7- Methoxy-4-oxaheptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5- Ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 1-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 1-ethoxy-4,8-dioxaundecyl, 15- Ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl.

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

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

Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino. The term "functional groups" is to be understood as meaning, for example, the following: carboxy, carboxamide, hydroxy, di- (C 1 -C ₄ -alkyl) -amino, C 1 -C ₄ -alkyloxy-carbonyl, cyano or C 1 -C ₄ -alkoxy C 1 -C ₄ -alkyl methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

Optionally C6-C4-aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles are, for example, phenyl, ToIyI, XyIyI, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl nyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylsaphthyl, 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, methoxyethyl phenyl or ethoxymethylphenyl.

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

A five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle is, for example, furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzthiazolyl, 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. compounds and the pseudohalogens, the group of carboxylic acids, the group containing SO ₄ ^{2 "} , SO ₃ ^2" , R ³ OSO ₃ ^" and R ³ SO ₃ -, and the group containing PO ₄ ^3" and R ³ R ⁰ PO ₄ -.

Particularly preferred anions are chloride, bromide, iodide, SCN, OCN, CN, acetate, propionate, benzoate, C 1 -C ₄ -alkyl sulfates, R ³ -CO 2 ^" , R ³ SO ₃ -, R ³ R ^b PO ₄ , Methanesulfonate, tosylate or di- (Ci-C ₄ -alkyl) phosphates. Particularly preferred anions are Ch, 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-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3- dimethyl imidazolium, 1,4-dimethyl imidazolium, 1,3,4-trimethyl imidazolium, 1,4-dimethyl-3-ethyl imidazolium, 1,4-dimethyl-3-butyl imida Zolium, 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, the group containing SO ₄ ^{2 "} , SO ₃ ^2" , R ³ OSO ₃ - and R ³ SO ₃ -, and the group containing PO ₄ ^{3 "} and R ³ R ^b PO ₄ -.

In particular, preferred anions are SCN, OCN, CN, acetate, propionate, benzoate, C 1 -C ₄ -alkyl sulfates, R ³ -C00 ^" , R ³ SO ₃ -, R ³ R ^b PO ₄ -, methanesulfonate, Tosylate or di- (Ci-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 ethyl imidazolium, 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-dimethylimidazole olium,

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 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 a further particularly preferred embodiment, ionic liquids are used whose anions are selected from the group of halides.

Preferred anion is in particular chloride.

[A] _n ⁺ 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octylimidazolium, 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) -S-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -S-ethylimidazolium , 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl-1-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3- ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl-S-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium , 1- (1-Butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethyl-imidazolium, 1- (1-octyl) -2,3-di - Methylimidazolium, 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 ³ PO ₄ -, in particular 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 ethyl imidazolium, 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-dimethylimidazo lium, 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,

[Y] ^{n +} HSO ₄ -,

used.

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

In a further embodiment according to the invention it is possible to use an ionic liquid of the formula II or a mixture of ionic liquids of the formula II, preferably an ionic liquid of the formula II is used.

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

In the process according to the invention, in step A) the targeted degradation of the cellulose is carried out in the presence of an acid, optionally with the addition of water (step A1) or at elevated temperature, if appropriate in the presence of water (step A2).

In step A1, acids, inorganic acids, organic acids or mixtures thereof can be used as acids.

Examples of inorganic acids are hydrogen halides, such as HF, HCl, HBr or Hl, perhalogenic acids such as HCIO ₄ , halogen acids such as HCIO3, sulfur-containing acids such as HaSO ₄ , polysulfuric acid or H2SO3, nitrogen-containing acids such as HNO3, or Phosphorus-containing acids, such as

HaPO ₄ , polyphosphoric acid or H ₃ PO ₃ Preferably hydrogen halide acids, such as HCl or HBr, HaSO ₄ , HNθ 3 θder HsPO ₄ are used, in particular HCl, H ₂ SO ₄ or H ₃ PO ₄ .

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-resp. 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 Ci-Cδ-haloalkanecarboxylic acids, e.g. Fluoroacetic acid, chloroacetic acid, bromoacetic acid, difluoroacetic acid, dichloroacetic acid, chlorofluoroacetic acid, trifluoroacetic acid, trichloroacetic acid, 2-chloropropionic acid, perfluoropropionic acid or perfluorobutane carboxylic 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 8 -haloalkanesulfonic acids, such as trifluoromethanesulfonic acid,

Aromatic sulfonic acids, for example arylsulfonic acids, such as benzenesulfonic acid or 4-methylphenylsulfonic acid.

Preferably, as organic acids, C 1 -C 6 -alkanecarboxylic acids, for example acetic acid or propionic acid, halogenated carboxylic acids, for example C 1 -C 6 -haloalkanecarboxylic acids, e.g. 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-Methylphenylsulfonsäure used. Preferably, acetic acid, chlorofluoroacetic acid, trifluoroacetic acid, perfluoropropionic acid, methanesulfonic acid, trifluoromethanesulfonic acid or 4-methyl-phenylsulfonic acid are used.

In a particular embodiment of the invention, the acid used is sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid or 4-methylphenyl used sulfonic acid. If 4-methylphenylsulfonic acid monohydrate is used, there is already one equivalent of water present.

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

In a further particular embodiment, ionic liquids and acids are used whose anions are not identical.

In step B, acylating agents are used. Acylating agents in the context of the present invention are carboxylic acid derivatives and also ketenes and diketenes.

Carboxylic acid derivatives in the context of the present invention are carboxylic acid derivatives of the formula IV

O

R X (IV)

where the radicals have the following meaning:

R ^x , R ^{x '} H, d-Cao-alkyl, C ₂ -C ₃ o-alkenyl, C ₂ -C ₃ O-Al kinyl, C ₃ -C ₂ -cycloalkyl, C ₅ -C ₂ -cycloalkenyl, aryl or heterocyclyl, where these seven latter radicals may be optionally substituted;

X is halogen, imidazol-1-yl or O-COR ^{x '} .

Ketenes for the purposes of the present invention (compounds of the formula V) are ketylenes of the formula Va and diketenes for the purposes of the present invention are diketenes of the formula Vb1 or mixed diketenes of the formula Vb2,

Va Vh 1 Vb2

where the radicals have the following meaning: R ^y, R ^{y ',} R ^z, R ^z' is hydrogen, Ci-C ₃ -alkyl, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ -alkynyl, C ₃ -C ₂ - cycloalkyl, C5 -Ci ₂ -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 Jq -Y- (CH ₂ Jr or a -CH = CH- CH = CH- chain, where

YO, S, S (= O), S (= O) _2, NH or NCi-C ₆ alkyl; o is O or i; p is 2, 3, 4, 5, 6, 7 or 8; q, r is 1, 2, 3, 4, 5 or 6;

mean.

As the optionally ₃₀ alkyl radicals for R ^x, R ^{x ',} ^y R, ^{y R',} R ^z and R are substituted Ci-C ^{z 'in} particular, unsubstituted Ci-C ₃ -alkyl groups or by functional groups, Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted Ci-C ₃ o-alkyl radicals, preferably Ci-C ₃ o-alkyl radicals, 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, 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, by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted Ci-C ₃ -alkyl radicals, 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-phenoxypropyl, 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) + (ib) 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) ₊ i, C ₆ Fi ₃ , C ₈ Fi ₇ , C10F21, C ₂ F _25), chloromethyl, 2-chloroethyl, trichloromethyl, 1, 1-dimethyl-2-chloroethyl, methylthiomethyl, ethylthiomethyl, butyl tylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa- pentyl, 8-hydroxy-3,6-dioxo-octyl, 1 1-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 1 1-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-dioxa-tetradecyl, 5- Methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1 1-

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

As optionally substituted C ₂ -C ₃ o-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 substituted C2-C3o-alkenyl radicals, preferably C2-C3o-alkenyl radicals, such as vinyl, 2-propenyl, 3-butenyl, cis- 2-butenyl or trans-2-butenyl, more preferably vinyl or 2-propenyl; or C 2 -C 30 -alkenyl radicals which are preferably substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, C _m F 2 ( _m -a) - (ib) H 2a-b in <30, 0 <a <m and b = 0 or 1.

As optionally substituted C ₂ -C ₃ o-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 substituted C2-C3o-alkynyl radicals called, preferably C2-C3o-alkynyl radicals, such as ethynyl, 1-propyn-3-yl, 1-

Propyn-1-yl or 3-methyl-1-propyn-3-yl, more 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 Cs-Cβ-cycloalkyl radicals or by functional Ie groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles called substituted C3-Ci2-cycloalkyl radicals, preferably C3-Ci2-cycloalkyl radicals, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl , Cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl or butylcyclohexyl, and bicyclic systems such as norbornyl, preferably cyclopentyl or cyclohexyl; or preferably substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, C 3 -C 12 -cycloalkyl radicals, such as, for example, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F2 ( _m -a) - (ib) H2a-b with m <30, 0 <a <m and b = 0 or 1.

As optionally substituted C ₅ -C ₂ -cycloalkenyl radicals for R ^x , R ^{x '} , R ^y , R ^y' , R ^z and R ^{z '} are in particular unsubstituted Ca-Cβ-cycloalkenyl radicals or by functional groups, aryl , Alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles called substituted Ca-Cs-cycloalkenyl radicals, preferably Ca-Cs-cycloalkenyl radicals, such as 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2 , 5-Cyclohexadienyl, and bicyclic system such as norbornyl, more preferably 3-cyclopentenyl, 2-cyclohexenyl or 3-cyclohexenyl; or preferably Ca-Cβ-cycloalkenyl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles

Radicals, such as C _n F2 _(m -a) -3 (ib) H2a-3b in the <12, 0 <a <m and b = 0 or the first

As optionally substituted aryl radicals for R ^x , R ^{x '} , R ^y , R ^y' , R ^z or R ^{z '} are in particular unsubstituted C6-Ci2-aryl radicals or by functional groups, aryl, alkyl, aryloxy, alkyloxy , Cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C6-Ci2-aryl radicals, preferably C6-Ci2-aryl radicals, such as phenyl, α-naphthyl or ß-naphthyl, more preferably phenyl; or preferably C6-C12-aryl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as ToIyI, XyIyI, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl , Dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C6F ( _5-a ) Ha with 0 <a <5, particularly preferably 4-toluene.

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 contain oxygen, nitrogen and / or sulfur atoms, such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl or benzothiazolyl; or preferably by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted 5- or 6-membered heteroaryl radicals having 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 ₀ - (CH ₂ ) _P -, - (CH ₂ ) qY- (CH ₂ ) r or a -CH = CH-CH = CH- chain, are preferably a -Yo (CH ₂ ) _P -, - (CH ₂ ) _q -Y- (CH ₂ ) r or a -CH = CH-CH = CH- chain, especially

- (CH ₂ ) S-, - (CH ₂ ) ₆ - or -CH = CH-CH = CH-, in particular - (CH ₂ ) ₅ - or - (CH ₂ ) ₆ -, in

Consideration or by Ci-C ₄ alkyl-substituted -Y _o - (CH ₂₎ _P -, - (CH ₂₎ _q -Y- (CH ₂₎ _r or by

Ci-C ₄ alkyl-substituted -CH = CH-CH = CH- chain, into consideration.

In one embodiment of the present invention, carboxylic acid derivatives of the formula IV are used.

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 6 -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.

R ^x ., R ^{x 'is} hydrogen or C 1 -C 6 -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").

R ^{x is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;

X OCOR ^X.

In a further embodiment of the present invention, ketenes of the formula Va are used.

In particular, ketenes of the formula Va are used, where the radicals have the following meanings:

R ^{y is} hydrogen or C 1 -C 6 -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 of the present invention, diketenes of the formula Vb1 are used.

In particular, diketenes of the formula Vb1 are used, where the radicals have the following meanings:

R ^{y is} hydrogen or C 1 -C 6 -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 of the present invention, mixed diketenes of the formula Vb2 are used.

In particular, mixed diketenes of the formula Vb2 are used, where the radicals have the following meanings:

R ^y , R ^{y is} 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.

Celluloses from a variety of sources, such as e.g. cotton, flax, ramie, straw, bacteria etc., or wood or bagasse, in the cellulose-enriched form.

In the process according to the invention, however, not only cellulose can be used, but generally a poly- or an oligosaccharide. Examples of polysaccharides, besides cellulose and hemicellulose, include starch, glycogen, dextran and tunicin. Likewise, these include the polycondensates of D-fructose, such as inulin, and u.a. Chitin and alginic acid. The corresponding explanations apply accordingly.

In one embodiment of the present invention, a polysaccharide, e.g. Cellulose, hemicellulose, starch, glycogen, dextran, tunicin, inulin, chitin or alginic acid, preferably cellulose.

In the process according to the invention, a solution of cellulose in ionic liquid is prepared. The concentration of cellulose can be varied within wide ranges. Usually, it is in the range of 0.1 to 50 wt .-%, based on the total weight of the solution, preferably 0.2 to 40 wt .-%, particularly preferably 0.3 to 30 wt .-% and particularly preferably at 0.5 to 20% by weight.

This dissolution 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, particularly preferably at 50 to 150 ° C. , But it is also possible to accelerate the dissolution process by intensive stirring or mixing and by entry of microwave or ultrasonic energy or by combining them.

This solution is now used in step A1) or in step A2). In the inventive step A1), the targeted degradation in the presence of an acid, optionally carried out with the addition of water.

As acids, inorganic acids, organic acids or mixtures thereof are used, as described above.

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

As already described above, the cellulose is dissolved in the ionic liquid. To this solution thus obtained, the acid and optionally water is added. The addition of water may be necessary if the adhering to the cellulose used water is not sufficient to achieve the desired degree of degradation. As a rule, the proportion of water in conventional cellulose is in the range from 5 to 10% by weight, based on the total weight of the cellulose used (cellulose per se + adhering water). For a partial degradation of the cellulose, the corresponding stoichiometrically necessary amounts of water and acid are added, which are necessary to achieve a corresponding DP value. However, it is also possible to use excess water and acid and to stop the reaction when the desired degree of degradation has been achieved.

In another embodiment, the ionic liquid, acid and possibly water are premixed and the cellulose is dissolved in this mixture.

There is also the possibility that one or more further solvents are added to the reaction mixture or are already added with the ionic liquid and / or the acid and / or optionally the water. Suitable solvents here are those which do not adversely affect the solubility of the cellulose, such as aprotic-dipolar solvents, for example dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.

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

Depending on the ionic liquid and the acid used, the hydrolysis is usually carried out at a temperature of the melting point of ionic liquid to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C.

Usually, the reaction is carried out at ambient pressure. However, it may also be advantageous on a case-by-case basis to work at overpressure, especially when 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 N2, a noble gas or a mixture thereof to work.

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 optionally the reaction temperature is set.

If it is desired to convert the cellulose, which is composed on average of x anhydroglucose units, into a cellulose whose number of hydro-glucose units is less than x, the amount of water used and acid used is usually adjusted in accordance with the degree of degradation ( ΠAΠ- hydroglucose units / acid> 1). J ^β greater than the quotient nAnhydroglucoseeinheiten / nSaure is, d ^β StO lower will be under otherwise the same reaction conditions and the same reaction time, the average degradation of cellulose. The larger the quotient nAnhydrogiuΣseem- heiten / nwasser, the lower will be under otherwise the same reaction conditions and the same reaction time, the average degradation of cellulose.

It is also possible to stop the hydrolysis reaction when the desired degree of degradation is achieved by trapping the acid with a base. Suitable bases include both inorganic bases, e.g. Alkali hydroxides, carbonates, hydrogen carbonates, but also organic bases such as e.g. Amines, which are used in stoichiometric ratio to the acid or in excess. In a further embodiment, a hydroxide can be used as the base, which is characterized in that its cation corresponds to that of the ionic liquid used.

It is also possible to stop the degradation reaction when the desired degree of degradation is achieved by adding appropriate amounts of acylating agent which will react with the remaining water.

This solution thus obtained is now used in step B).

As an alternative to step A1), step A2) can also be carried out. In the inventive step A2), the cellulose is optionally treated with the addition of water at elevated temperature.

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

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 - and R ³ SO ₃ ^" , as well as 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 ³ SO ₃ ^" , R ^a R ^b PO ₄ ^" , Methanesulfonate, tosylate or C 1 -C ₄ -dialkylphosphates; and particularly preferred anions are Cl ^", CH ₃ ^COO," C2H5COO ^", 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 ³ PO ₄ -, in particular HSO ₄ -.

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

In one embodiment, the preparation of the reaction solution and the degradation are carried out at the same temperature.

In a further embodiment, the preparation of the reaction solution and the degradation are carried out at different temperatures.

It is also possible on a case-by-case basis that degradation of the cellulose takes place already during the preparation of the reaction solution. In a special embodiment, the dissolution and degradation processes take place more or less in parallel.

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.

Depending on the desired degree of degradation, the reaction time and the reaction temperature are adjusted. In one embodiment, water is added, preferably in substoichiometric amounts, or an excess of water is used and the reaction is stopped.

When the degradation is carried out in the presence of water, it is possible to premix the ionic liquid and the water and dissolve the cellulose in this mixture. But it is also possible to add 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 hydro-glucose units is less than x, the amounts of water used are usually adjusted in accordance with the degree of degradation (n-anhydroglucose units) ^> 1). The larger the quotient nAnhydrogiuΣseemheiten / nwasser, the lower will be under otherwise the same reaction conditions and the same reaction time, the average degradation of cellulose and the higher the DP of the degraded cellulose (of course, will be smaller than the DP of the cellulose used).

In another embodiment, working without the addition of water. This is usually the case when the ionic liquid used contains small amounts of water and / or if water adheres to the cellulose used. The proportion of water in conventional cellulose can be up to 10% by weight, based on the total weight of the cellulose used. The above explanations apply accordingly.

There is also the possibility that one or more other solvents are added to the reaction mixture or the water - as far as it has been added. Suitable solvents here are those which do not adversely affect the solubility of the cellulose, such as aprotic dipolar solvents, for example dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.

Furthermore, it is possible to terminate the degradation reaction when the desired degree of degradation is achieved by adding appropriate amounts of acylating agent which will react with any remaining water.

The solution thus obtained is now used in step B). The acylating agent is added to the solution obtained from step A).

The carboxylic acid derivative of the formula IV or the ketene of the formula V can be added in bulk, dissolved in an ionic liquid or in a suitable solvent. Suitable solvents are, for example, ethers, such as diethyl ether, methyl tert-butyl ether, terahydrofuran or dioxane, or ketones, such as dimethyl ketone, or halogenated hydrocarbons, such as dichloromethane, trichloromethane or dichloroethane. The amount of solvent used to dissolve the carboxylic acid derivative of formula IV or the ketene of formula V should be such that no precipitation of the cellulose occurs upon addition. As ionic liquid is preferably the one in which the cellulose itself - as described above - is dissolved.

If the carboxylic acid derivative of the formula IV or the ketene of the formula V is gaseous, this can be gassed into the solution of cellulose in the ionic liquid.

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

In a further particular embodiment, the carboxylic acid derivative of the formula IV or the ketene of the formula V is added dissolved in an ionic liquid, with particular preference being given to using the ionic liquid which is also used to dissolve the cellulose.

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. Furthermore, nitrogen-containing bases, such as pyridine, etc., can also be added.

In a particular embodiment, in addition to the ionic liquid and optionally the solvent in which the carboxylic acid derivative of the formula IV or the ketene of the formula V is dissolved, the reaction mixture contains less than 5% by weight, preferably less than 2% by weight, in particular less than 0.1% by weight, based on the total weight of the reaction mixture, of further solvents and / or additional nitrogen-containing bases. In the event that carboxylic acid derivatives of the formula IV with X =Hal or OCOR ^{X '} are used as the acylating agent, it may also be expedient to carry out the acylation in the presence of a tertiary amine such as, for example, triethylamine, an aromatic nitrogen base such as pyridine, or Mixtures thereof. 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 -alkane carboxylic acids or of 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, ie 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.

Depending on the ionic liquid used and the carboxylic acid derivative of the formula IV or the ketene of the formula V used, the reaction is usually carried out at a temperature of the melting point of the ionic liquid up to 200 ° C., preferably from 20 to 180 ° C., in particular 50 up to 150 ° C performed.

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 N2, a noble gas or mixtures thereof, to work.

In the case of carboxylic acid derivatives of the formula IV or ketene of the formula V which are gaseous at the reaction temperature, it may be advantageous to carry out the reaction under the autogenous pressure of the reaction mixture at the desired reaction temperature or at a pressure which is higher than the autogenous pressure of the reaction system ,

However, it can also be advantageous to react with a carboxylic acid derivative of the formula IV or a ketene of the formula V which is gas at the reaction temperature. is shaped to perform under ambient pressure and to use the gaseous carboxylic acid derivative of formula IV or the ketene of formula V in excess.

Depending on the desired degree of substitution of the cellulose, the amount of acylating agent used - in each case in relation to the cellulose used - the reaction time and optionally the reaction temperature is set.

For example, if it is desired to completely acylate the cellulose, which is composed on average of u anhydroglucose units, then 3u equiva- lent acylating agents are needed. Preferably, the stoichiometric amount of acylating agent (nAzyiierungsmittei / nAnhydrogiucoseeinheiten = 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 (acylating agent / anhydrogucose units <3). The smaller the quotient of the 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 is achieved by separating the acylated cellulose 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, e.g. a lower alcohol, such as methanol, ethanol, propanol or butanol, or with a ketone, for example diethyl ketone, etc., or mixtures thereof. 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 precipitating the acylated cellulose as described above and filtering off the acylated cellulose. But it is also possible to carry out the separation by centrifugation. From the filtrate or the centrifugate can be recovered by conventional methods, the ionic liquid keits 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 be reused in the process according to the invention.

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, however, is slightly soluble, such as a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, such as diethyl ketone, etc., or mixtures thereof, initiate and depending on the embodiment, for example, fibers to obtain films of acylated cellulose. The choice of the suitable solvent is also determined by the respective degree of substitution and the substituents of the cellulose. The filtrate is worked up as described above.

Furthermore, it is possible to terminate the acylation reaction when the desired degree of acylation is achieved by cooling and working up the reaction mixture. The work-up can be carried out according to the methods described above.

The termination of the acylation reaction can also be carried out in such a way that acylating agent still present at a given time is removed from the reaction mixture by distillation, stripping or extraction with a solvent which forms two phases with the ionic liquid.

In a further embodiment of the present invention, two or more acylating agents are used. In this case, a mixture of two (or more) carboxylic acid derivatives of the formula IV or ketenes of the formula V can be used in analogy to the above procedure. However, it is also possible first to carry out the reaction with a first acylating agent up to a DS = a (<3) and then to carry out the reaction with a second acylating agent up to a DS = b, where a <b <3.

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

In the event that the ionic liquid is recycled, in one embodiment the ionic liquid is purified, for example, freed from the precipitant, optionally added further solvents, hydrolysis and degradation products of the acylating agent, etc., and used again in step A) , In a further embodiment, the ionic liquid, which can be up to 15

Wt .-%, preferably up to 10 wt .-%, in particular up to 5 wt .-% of precipitant (s), etc. as described above contains, are used in step A). This may, however, 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), is freed from precipitants still present, for example by still adding existing precipitant, etc. is distilled off, or it is a corresponding excess of acylating agent used. The process can be carried out batchwise, semicontinuously or continuously.

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] ⁺ [Y] "^" ), or of the formulas IIa, b or c ([A ¹ ] ⁺ [A ² ] ⁺ [Y] ⁿ -, where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] "-), where n = 3; [A ¹ J ⁺ [A ² J ⁺ [A ³ J ⁺ [A ⁴ J ⁺ [Y] ⁿ -, where n = 4), where [A] _n ⁺ , [A ¹ J ⁺ , [[A ² J ⁺ , [[A ³ J ⁺ , [A ³ J ⁺ , [A ⁴ J ⁺ ] as defined above and [where [Y] ^p - may be selected from

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

• the group of carboxylic acids of the general formula: R ³ COO-

The group of borates of the general formula: BO ₃ ^{3 "} , HBO ₃ ^2" , H ₂ BO ₃ -, R ³ R ^b BO ₃ -, R ³ HBO ₃ -, R ³ BO ₃ ^{2 "} , B (0R ³ ) (0R ^b ) (0R ^c ) (0R ^d ) -,

B (HSO ₄ ) -, B (R ³ SO ₄ ) -

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

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

the group of methides of the general formula:

SO ₂ -R ³

R ^b -O ₂ S SO ₂ -R ^C

The meaning of the variable is as defined above. Likewise, the embodiments and procedures described above apply analogously.

The following examples serve to illustrate the invention.

Preamble:

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

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

Abbreviations: BMIM CI 1-butyl-3-methylimidazolium chloride

BMIM Ac 1-butyl-3-methylimidazolium chlorideDS 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-toluenesulfonic acid monohydrate, the mixture was stirred at 100 ° C. for 6 hours. To the mixture was then added 3.0 g of acetic anhydride and stirred for a further 16 hours at 100 ° C. 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, 1 ml of BMIM Ac was added under argon at 100 ° C. to 1.072 g Avicel PH 101 in 1 and the mixture was stirred for 2 hours until a clear solution had formed. After addition of 4.0 g of acetic anhydride was stirred at 100 ° C for 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 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

claims

1. A process for the acylation of poly- or oligosaccharides, characterized in that one dissolves a polysaccharide 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), treated and in step B), the polysaccharide or oligosaccharide, whose DP is lower than that of the polysaccharide or oligosaccharide used, reacted with an acylating agent.

2. The method according to claim 1, characterized in that one uses as polylactic or Ologosaccharid a polysaccharide.

3. The method according to claim 2, characterized in that one uses as the polysaccharide cellulose.

4. Process according to claims 1 to 3, characterized in that the ionic liquid, or mixtures thereof, are selected from the compounds of the formulas I,

[A]; [Y] ⁿ - (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 "represent} a mono-, di-, tri- or tetravalent anion;

or

the compounds of the formula II

[A ¹ ] ⁺ [A ² ] ⁺ [Y] "- (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

in which [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ⁺ independently of one another are those mentioned for [A] ⁺

Groups are selected; 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 the formulas (IIIa) to (MIy)

(purple) (MIb) (MIc)

(MId) Ie) (MIf)

Cing) (mg ¹ ) (MIh) (MIi) (NU) (MIj ')

(MIk) (MIk ') (IUI)

(Ulm) (MIm ') (MIn)

(MIn ') (MIo) (MIo')

(MIp) (MIq) (MIq ')

(HIq ") (Me) (MIr ')

(MIr ") (MIs) (With)

(MIu) (MIv) (MIw)

R ^z R ^z

3 I ⁺ 1 I +

R-P-R S-R I R R

Ix) (MIy)

and oligomers containing this structure, wherein

the radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms; and the radicals R ¹ to R ⁹ independently of one another represent 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 with 1 to 20

Carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (IM) are bonded to a carbon atom (and not to a heteroatom) may additionally be halogen or a functional group; or

two adjacent radicals from the series R ¹ to R ⁹ together also for a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups pen or substituted Rest with 1 to 30 carbon atoms, can stand.

6. Process according to claims 4 or 5, characterized in that [Y] ⁿ "is selected from an anion

the group of halides: F, Cl, Br, I

Group of halogen-containing compounds of the formula: F, Cl, Br, h, BF ₄ ^" , PF ₆ ^" , CF ₃ SO ₃ ^" , (CF ₃ SOs) ₂ N-, CF ₃ CO ₂ -, CCI ₃ CO ₂ , CN ^" ,

SCN, OCN

The group of phosphonites and phosphinites of the general formula:

R ³ R ^b PO ₂ -, R ³ HPO ₂ -, R ³ R ^b P0-, R ³ HPO ^" the group of carboxylic acids of the general formula: R ³ COO-

the group of borates of the general formula: BO ₃ ^{3 "} , HBO ₃ ^2" , H ₂ BO ₃ -, R ³ R ^b BO ₃ -, R ³ HBO ₃ -, R ³ BO ₃ ^{2 "} ,

B (0R ³ ) (0R ^b ) (0R ^c ) (0R ^d ) -, B (HSO ₄ ) ^" , B (R ³ SO ₄ ) ^"

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

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

The group of the alkyl or aryl silane salts of the general formula:

R ³ SiO ₃ ³ -, R ³ R ^b Si0 ₂ ² -, R ³ R ^b R ^c Si0 ^" , R ³ R ^b R ^c SiO ₃ -, R ³ R ^b R ^c Si0 ₂ -, R ³ R ^b Si0 ₃ ² -

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

the group of methides of the general formula:

SO ₂ -R ³

R ^b -O ₂ S SO ₂ -R ^C

wherein the radicals R ³ , R ^b , R ^c and R ^d are each independently hydrogen, Ci-C ₃ o-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 8 -alkyl, C ₆ -C 14 -aryl, Cs

Ci ₂ -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, wherein two of them together an unsaturated, saturated or aromatic, optionally by one or more oxygen and / or sulfur atoms and / or a or a plurality of unsubstituted or substituted imino-interrupted ring each of said radicals may additionally be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles;

stands.

7. Process according to claims 4 to 6, characterized in that [A] ⁺ for a cation selected from the group of the compounds IMa, Nie, MIf; IMg, IMg, MIh, Uli, MIj, MIj, MIk, IMk, IUI, Ulm, Ulm, IMn or IMn.

8. Process according to claims 4 to 7, characterized in that [A] ^{+ represents} a cation selected from the group of the compounds IMa, IMe or IMf.

9. The method according to claims 4 to 8, characterized in that [Y] ⁿ "for an anion selected 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 ³ OSO ₃ - and R ³ SO ₃ -, and the group containing PO ₄ ^3" and R ³ R ^b PO ₄ -, stands.

10. The method according to claims 1 to 9, characterized in that as step A) step A1) is performed.

1 1. A method according to claim 10, characterized in that are used as the acid, an inorganic acid, an organic acid or mixtures thereof.

12. The method according to claims 1 to 9, characterized in that as step A) step A2) is performed.

13. The method according to claims 1 to 12, characterized in that in step B) as the acylating agent, a carboxylic acid derivative of the formula IV

where the radicals have the following meaning:

R ^x, R ^{x 'is} H, Ci-C ₃₀ alkyl, C ₂ -C ₃₀ -alkenyl, C ₂ -C ₃₀ -alkyl kinyl, _{_C3-Ci2} cycloalkyl, C ₅ - C ₂ cycloalkenyl, aryl or Heterocyclyl, where these seven latter radicals may be optionally substituted; X is halogen, imidazol-1-yl or O-COR ^{X '} ;

or

a ketene of the formula Va or a diketene of the formula Vb1 or a mixed diketene of the formula Vb2

Va Vb1 Vb2

where the radicals have the following meaning:

R ^y, R ^{y ',} R ^z, R ^z' is hydrogen, Ci-C ₃ -alkyl, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ O-AI kinyl C ₃ -C ₂ - cycloalkyl, C5 -Ci ₂ -cycloalkenyl, aryl or heterocyclyl, where the seven last-mentioned radicals may optionally be 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 Jr or a -CH = CH- CH = CH- chain, where

Y is O, S, S (O), S (O) ₂ , NH or NCi-C ₆ alkyl; o is O or 1; p is 2, 3, 4, 5, 6, 7 or 8; q, r is 1, 2, 3, 4, 5 or 6;

mean;

starts.

14. The method according to claim 13, characterized in that the acylating agent used is a carboxylic acid derivative of the formula IV.

15. Process according to claim 14, characterized in that the acylating agent used is a carboxylic acid derivative of the formula IV where X = halogen, preferably chloride.

16. The method according to claim 14, characterized in that a carboxylic acid derivative of formula IV with X = OCOR ^{X '} , preferably with OCOR ^X used as acylating agent.

17. The method according to claim 13, characterized in that a ketene of the formula V is used as the acylating agent.

18. The method according to claims 1 to 17, characterized in that the initial concentration of polysaccharide or oligosaccharide, in ionic liquid in a range of 0.1 to 50 wt .-% based on the total weight of the solution.

19. Process according to claims 1 to 18, characterized in that steps A and B are carried out at a temperature from the melting point of the ionic liquid to 200 ° C.

20. Process according to claims 1 to 19, characterized in that the acylated poly- or oligosaccharide obtained in the acylation in step B) is quenched by the addition of a solvent in which the acylated polysaccharide is insoluble.

21. Process for the acylation of poly- or oligosaccharides, characterized in that the poly- or oligosaccharide in at least one ionic liquid of the formula I, IIa, IIb or Mc, where [A] _n ⁺ , [A ¹ ] ⁺ , [ A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ have} the meaning given in claim 4 and [Y] ⁿ "is selected from an anion

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 SOs) ₂ N-, CF ₃ CO ₂ -, CCI ₃ CO ₂ -, CN ^" , SCN -, OCN-

The group of phosphonates and phosphinates of the general formula:

R ³ H PO ₃ -, R ³ R ^b PO ₂ -, R ³ R ^b PO ₃ - the group of phosphites of the general formula: PO ₃ ^{3 "} , HPO ₃ ^2" , H ₂ PO ₃ -, R ³ PO ₃ ^{2 "} , R ³ HPO ₃ -, R ³ R ^b PO ₃ -

the group of phosphonites and phosphinites of the general formula: R ³ R ^b PO ₂ -, R ³ HPO ₂ -, R ³ R ^b P0 ^" , R ³ HPO ^"

the group of carboxylic acids of the general formula: R ³ COO-

The group of borates of the general formula:

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

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

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

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

the group of methides of the general formula:

SO ₂ -R ³

R ^b -O ₉ S ^' SO, -R ^C

wherein the radicals R ³ , R ^b , R ^c and R ^d are each independently hydrogen, Ci-C ₃ o-alkyl, optionally substituted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino interrupted C2-Ci8-alkyl, C6-Ci4-aryl, Cs-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, wherein two of them together an unsaturated, saturated or aromatic, optionally 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 can be substituted;

stands;

with a carboxylic acid derivative of the formula IV as described in claim 13.